Surfactant-containing acetoacetoxy-functional and enamine-functional polymers

ABSTRACT

Surfactant-containing acetoacetoxy-functional polymers (SAAP&#39;s) are described. The acetoacetoxy-functional polymer may be a surfactant-containing enamine-functional polymer and more preferably a surfactant-containing, polymeric (polyamino)enamine (PPAE). The PPAE is the reaction product of a surfactant-containing acetoacetoxy-functional polymer (SAAP) and a poly(alkylenimine). The polymers may be prepared as waterborne polymer compositions, such as latexes. The waterborne polymer compositions can be prepared with high solids content while maintaining low viscosity. Waterborne polymer compositions containing the polymers of the inventions are useful in a variety of coating formulations such as, for example, paints, inks, sealants, and adhesives. When used in coating formulations, the polymers of the invention provide adhesion and crosslinking in the final film or coating. The film or coating may be cured at ambient temperatures or may be thermally cured.

This application claims priority to U.S. Provisional Application Ser.No. 60/018,423, filed May 28, 1996; Ser. No. 60/018,424 filed May 28,1996; and Ser. No. 60/028,444 filed Oct. 10, 1996.

FIELD OF THE INVENTION

This invention belongs to the field of emulsion chemistry. Inparticular, it relates to acetoacetoxy-functional polymers which areuseful in a variety of coating formulations.

BACKGROUND OF THE INVENTION

In an increasing number of industries, aqueous coating compositionscontinue to replace traditional organic solvent-based coatingcompositions. Paints, inks, sealants, and adhesives, for example,previously formulated with organic solvents are now formulated asaqueous compositions. This reduces potentially harmful exposure tovolatile organic compounds (VOC's) commonly found in solvent-basedcompositions. While the move from organic solvent-based to aqueouscompositions brings health and safety benefits, the aqueous coatingcompositions must meet or exceed the performance standards expected fromsolvent-based compositions. The need to meet or exceed such performancestandards places a premium on the characteristics and properties ofwaterborne polymer compositions used in aqueous coating compositions.

Waterborne polymer having various functional groups have been used toimpart and achieve desired properties to a particular coatingcomposition. For example, a coating composition should exhibit good filmformation, print and block resistance, as well as adhesion and tensileproperties. Polymers having acetoacetoxy- and enamine-functional groupsrepresent one example of waterborne polymers which have such properties,may carry different functional groups, and are useful in aqueous coatingcompositions.

U.S. Pat. No. 5,296,530 discloses a quick-curing coating prepared from apolymer having acetoacetyl groups, in which substantially all of theacetoacetyl groups have been converted to enamine functional groups.This conversion occurs, for example, by treatment with ammonia or aprimary amine. Coatings so prepared cure more quickly under sunlight orultraviolet light than coatings which contain the acetoacetyl functionalpolymer but which have not been converted to an enamine form.

U.S. Pat. Nos. 5,484,975 and 5,525,662 describe the preparation ofpolymers containing functional acetoacetate groups and then, followingthe polymerization, reacting the acetoacetate group with a functionalamine to form an enamine. The resulting polymers are reported to have avariety of uses including coatings, sealants, adhesives, and saturantapplications.

U.S. Pat. No. 5,498,659 discloses polymeric formulations comprising anaqueous carrier, at least one polymeric ingredient, a non-polymericpolyfunctional amine, and a base. The polymeric ingredient has bothacid-functional and acetoacetoxy-type functional moieties. The aqueouspolymeric formulations produce crosslinked polymeric surface coatings ona substrate.

Japanese Patent 61-21171 describes a fast-curing adhesive consisting oftwo separate liquids. The first liquid is an aqueous solution and/oraqueous emulsion of a polymer compound containing an acetoacetyl group.The second liquid consists of polyethylenimine.

Even with current waterborne polymer formulations, a need remains forimproved aqueous coating compositions and waterborne polymers for use inthose compositions. In particular, a need exists for waterborne polymercompositions which may formulated as a single, stable composition butwhich undergo crosslinking upon film formation imparting one or moredesired properties to the resulting coating. The present invention meetssuch needs.

SUMMARY OF THE INVENTION

This invention provides a surfactant-containing acetoacetoxy-functionalpolymer (SAAP). In a preferred embodiment, the acetoacetoxy-functionalpolymer is a surfactant-containing enamine-functional polymer and morepreferably a surfactant-containing, polymeric (polyamino)enamine (PPAE).The PPAE is the reaction product of a surfactant-containingacetoacetoxy-functional polymer (SAAP) and a poly(alkylenimine). Thepolymers of the invention may be prepared as waterborne polymercompositions, such as latexes. The waterborne polymer compositions canbe prepared with high solids content while maintaining low viscosity.Waterborne polymer compositions containing the polymers of the inventionare useful in a variety of coating formulations such as, for example,paints, inks, sealants, and adhesives. When used in coatingformulations, the polymers of the invention provide adhesion andcrosslinking in the final film or coating. The film or coating may becured at ambient temperatures or may be thermally cured.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the affect of polymer particle size and percent solids onthe viscosity of a latex of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides polymers which may be used in awaterborne polymer composition, that is a composition containing apolymer and water. Waterborne polymer compositions include, but are notlimited to, latexes, dispersions, microemulsions, or suspensions.Waterborne polymer compositions are stable when stored at roomtemperature or moderately above room temperature (e.g., about 50 to 60°C.) and provide adhesion and crosslinking upon film formation whenapplied to a substrate. Yet, a film or coating formed with polymers ofthe invention may be cured at room temperature (ambient cure) or atelevated temperatures (thermal cure).

The polymers of the invention are generally prepared as particles,particularly in a waterborne composition. The particles may bestructured or unstructured. Structured particles include, but are notlimited to, core/shell particles and gradient particles. The averagepolymer particle size may range from about 25 to about 500 nm. Preferredaverage polymer particle sizes for small particles range from about 25to about 100 nm and more preferably from about 45 to about 80 nm. Forlarge particles, preferred average polymer particle sizes range fromabout 110 to about 450 nm.

The polymer particles generally have a spherical shape. In oneembodiment, the generally spherical polymeric particle may have a coreportion and a shell portion. The core/shell polymer particles may alsobe prepared in a multilobe form, a peanut shell form, an acorn form, ora raspberry form. It is further preferred in such particles that thecore portion comprises about 20 to about 80% of the total weight of saidparticle and the shell portion comprises about 80 to about 20% of thetotal weight of the particle.

Reacting a surfactant-containing acetoacetoxy-functional polymer (SAAP)with ammonia, a primary or secondary amine yields asurfactant-containing enamine-functional polymer of the invention. Apolymeric (polyamino)enamine (PPAE) results from the reaction of a SAAPwith a poly(alkylenimine). Polymeric (polyamino)enamines represent aparticularly preferred group of amino-functional polymers for use in awaterborne polymer composition according to the invention. These variouspolymers according to the invention, their preparation, and the relatedpreferred embodiments are discussed below.

The SAAP may be prepared by free radical emulsion polymerization of anon-acid vinyl monomer having an acetoacetoxy functionality such asthose of Formula (1) below with at least one non-self-polymerizing,surface-active vinyl monomer and other non-acid vinyl monomers. Thisaffords water-based dispersion of surfactant-containing polymerparticles with the polymer having pendant acetoacetoxy groups. As usedhere, a non-acid vinyl monomer is an ethylenically-unsaturated,non-carboxylic acid-containing monomer. A pendant acetoacetoxy group isnot strictly limited to those at the termini of the polymer. Pendantacetoacetoxy groups also include groups attached to the polymer'sbackbone and available for further reaction.

The SAAP preferably contains about 1 to about 40 weight percentacetoacetoxy-functional monomers such as those of Formula (1) below,about 0.05 to about 20 weight percent of at least onenon-self-polymerizing, surface-active vinyl monomer and about 60 toabout 90 weight percent of other non-acid vinyl monomers. The weightpercentage is based on the total amount of monomer. More preferably, theSAAP has about 10 to about 25 weight percent acetoacetoxy monomers,about 0.1 to about 10 weight percent of at least onenon-self-polymerizing, surface-active vinyl monomer and about 75 toabout 90 weight percent of other vinyl monomers.

The water-based emulsion polymerization to prepare the SAAP preferablyoccurs in the presence of a nonionic surfactant and an anionicsurfactant. The nonionic surfactant may be present in amounts rangingfrom about 0.25 to about 5 phr, and the anionic surfactant in amountsranging from about 0.1 to 1 phr. The unit "phr" defines the grams dryweight of the recited component, for example the surfactant, per 100grams dry weight of the resin, where the "resin" includes allpolymerization components excluding water. Aspects of this emulsionpolymerization and preferred embodiments are discussed below.

Any non-acid vinyl monomer having acetoacetoxy-type functionality may beused to prepare a polymer of the invention. Of such monomers, preferredmonomers are those of Formula (1).

    R.sup.1 --CH═C(R.sup.2)C(O)--X.sup.1 --X.sup.2 --X.sup.3 --C(O)--CH.sub.2 --C(O)--R.sup.3                          (1)

For an acetoacetoxy-type monomer of Formula (1), R¹ is a hydrogen orhalogen. R² is a hydrogen, halogen, C₁ -C₆ alkylthio group, or C₁ -C₆alkyl group. R³ is a C₁ -C₆ alkyl group. X¹ and X³ are independently 0,S, or a group of the formula --N(R')--, where R' is a C₁ -C₆ alkylgroup. X² is a C₂ -C₁₂ alkylene group or C₃ -C₁₂ cycloalkylene group.The alkyl and alkylene groups described here and throughout thespecification may be straight or branched groups. Preferred monomers ofFormula (1) are acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, acetoacetoxy(methyl)ethyl acrylate, acetoacetoxypropylacrylate, allyl acetoacetate, acetoacetamidoethyl (meth)acrylate, andacetoacetoxybutyl acrylate. Acetoacetoxyethyl methacrylate (AAEM)represents a particularly preferred monomer of Formula (1).

Suitable non-acid vinyl monomers which may be used, for example,include, but are not limited to, methyl acrylate; methyl methacrylate;ethyl acrylate; ethyl methacrylate; butyl acrylate; butyl methacrylate;isobutyl acrylate; isobutyl methacrylate; ethylhexyl acrylate;2-ethylhexyl methacrylate; octyl acrylate; octyl methacrylate; iso-octylacrylate; iso-octyl methacrylate; trimethylolpropyl triacrylate;styrene; α-methyl styrene; glycidyl methacrylate; carbodiimidemethacrylate; C₁ -C₁₈ alkyl crotonates; di-n-butyl maleate;di-octylmaleate; allyl methacrylate; di-allyl maleate; di-allylmalonate;methoxybutenyl methacrylate; isobornyl methacrylate; hydroxybutenylmethacrylate; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate;acrylonitrile, vinyl chloride; ethylene; vinyl ethylene carbonate; epoxybutene; 3,4-dihydroxybutene; hydroxyethyl (meth)acrylate;methacrylamide; acrylamide; butyl acrylamide; ethyl acrylamide; vinyl(meth)acrylate; isopropenyl (meth)acrylate; cycloaliphaticepoxy(meth)acrylates; and ethylformamide. Such monomers are described in "TheBrandon Worldwide Monomer Reference Guide and Sourcebook" SecondEdition, 1992, Brandon Associates, Merrimack, New Hampshire; and in"Polymers and Monomers", the 1996-1997 Catalog from Polyscience, Inc.,Warrington, Pa.

To increase polymer stability, a small amount (about 0.4 phr) of sodium2-acrylamido-2-methylpropane sulfonate, (AMPS), and other stabilizingmonomers may be incorporated into the SAAP. Adding such stabilizingmonomers to the polymer shell, for example, aids in preventingflocculation upon the addition of a polyalkylenimine to form a PPAE.High levels of such stabilizing monomers may create water membranelayers between polymer particles in the latex or disrupt film formation.AMPS is available from Pennwalt Corporation under the LUBRIZOL 2405Trade name.

Vinyl esters of the general Formula (2) represent further examples ofnon-acid vinyl monomers:

    RCH═CH--O--C(O)--C(R).sub.3                            (2)

In Formula (2), R is independently hydrogen or an alkyl group of up to12 carbon atoms. Particular monomers of Formula (2) include CH₂═CH--O--C(O)--CH₃, CH₂ ═CH--O--C(O)--C(CH₃)₃, CH₂ ═CH--O--C(O)--CH(C₂H₅)(C₄ H₉), and CH₂ ═CH--O--C(O)--CH₂ CH₃. Vinyl ester monomers alsoinclude vinyl esters of vinyl alcohol such as the VEOVA series availablefrom Shell Chemical Company as VEOVA 5, VEOVA 9, VEOVA 10, and VEOVA 11products. See O. W. Smith, M. J. Collins, P. S. Martin, and D. R.Bassett, Prog. Org. Coatings 22, 19 (1993).

As a further preferred embodiment, the SAAP may also incorporatenitrogen-containing, non-acid vinyl monomers known to promote wetadhesion. Exemplary wet adhesion monomers include, for example,t-butylaminoethyl methacrylate; dimethylaminoethyl methacrylate;diethylaminoethyl methacrylate; N,N-dimethylaminopropyl methacrylamide;2-t-butylaminoethyl methacrylate; N,N-dimethylaminoethyl acrylate;N-(2-methacrylamido-ethyl)ethylene urea; andN-(2-methacryloyloxy-ethyl)ethylene urea.N-(2-methacryloyloxyethyl)ethylene urea is available from RohmTech as50% solution in water under the Rohamere 6852-O trade name and as a 25%solution in water under the Rohamere 6844 trade name.N-(2-methacrylamido-ethyl)ethylene urea is available from Rhone-Poulencunder the WAM trade name.

Small amounts of acid vinyl monomers may also be used to prepare an SAAPaccording to the invention. Such acid vinyl monomers include, forexample, acrylic acid, methacrylic acid, itaconic acid, crotonic acid,and monovinyl adipate. Incorporating acid vinyl monomers into the SAAPmay increase the viscosity of the resulting latex and may have adetrimental effect on the formation of an enamine-functional polymeraccording to the invention. Generally these monomers are used in smallamounts. Preferably, the amount of acid vinyl monomers may range, forexample, from 0 to 5 phr. Greater amounts may be used to achieve adesired effect, such as increased viscosity.

Preparation of the SAAP reacts non-acid vinyl monomers, such asdescribed above, with at least one non-self-polymerizable,surface-active vinyl monomer (also known as a non-self-polymerizableethylenically-unsaturated surfactant or a reactive surfactant). Anon-self-polymerizable surfactant monomer, rather than polymerizing withitself to form a separate polymeric surfactant, is substantially(preferably completely) incorporated into the polymer of the invention.Thus, the surfactant becomes part of the polymer. Non-self-polymerizingsurfactants possessing, for example, propenylphenyl or allyl groups arepreferred. Examples include surface active monomers sold by PPGIndustries, Inc., as MAZON® SAM 181, 183, 184, 211 surfactants which areanionic sulfates or sulfonates and MAZON® SAM 185-187 surfactants whichare nonionic surfactants. Other non-self-polymerizing, surface-activevinyl monomers include the macro monomers sold by Daiichi Kogyo Seiyakuunder the names NIOGEN RN, AQUARON or HITENOL surfactants. These includepolyoxyethylene alkyl phenyl ether compounds of the general formulae(3), (4), and (5): ##STR1## In Formulae (3), (4), and (5), R is nonyl oroctyl and n and m are preferably integers of from 15 to 50 and 15 to 40,respectively. More preferably, n ranges from 20 to 40, and m from 15 to25. HITENOL RN, HITENOL HS-20 and HITENOL A-10 products are particularlypreferred non-self-polymerizing, surface-active monomers. Other suchpolymerizable surfactants include the sodium alkyl allyl sulfosuccinatesold by Henkel, under the trade name TREM LF-40 surfactant.

The SAAP (as well as other polymers useful in the invention) may beprepared using emulsion polymerization techniques known in the art. Thepolymer may, as is known in the art, be prepared using free radicalemulsion polymerization techniques which yield structured orunstructured particles. As mentioned above, structured particlesinclude, for example, core/shell particles, raspberry particles, andgradient particles. Chain transfer agents, initiators, reducing agents,buffers, and catalysts, known in the art of emulsion polymerization, maybe used to prepare the polymers.

Exemplary chain transfer agents are butyl mercaptan, dodecyl mercaptanmercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, n-butyl3-mercaptopropionate, octyl mercaptan, isodecyl mercaptan, octadecylmercaptan, mercaptoacetic acid, allyl mercaptopropionate, allylmercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate, andthe reactive chain transfer agents taught in U.S. Pat. No. 5,247,040,incorporated here by reference. In particular, 2-ethyihexyl3-mercaptopropionate represents a preferred chain transfer agent.

Typical initiators include hydrogen peroxide, potassium or ammoniumperoxydisulfate, dibenzoyl peroxide, lauryl peroxide, ditertiary butylperoxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide, benzoylperoxide, and the like.

Suitable reducing agents are those which increase the rate ofpolymerization and include for example, sodium bisulfite, sodiumhydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid,isoascorbic acid, and mixtures thereof.

Polymerization catalysts are those compounds which increase the rate ofpolymerization and which, in combination with the above describedreducing agents, may promote decomposition of the polymerizationinitiator under the reaction conditions. Suitable catalysts includetransition metal compounds such as, for example, ferrous sulfateheptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobaltacetate, cobaltous sulfate, and mixtures thereof.

As discussed above, the emulsion polymerization to prepare the SAAPpreferably occurs in water and in the presence of a nonionic surfactantand/or an anionic surfactant. Suitable nonionic surfactants includesurfactants such as alkyl polyglycol ethers such as ethoxylationproducts of lauryl, oleyl, and stearyl alcohols; alkyl phenol polyglycolethers such as ethoxylation products of octyl- or nonylphenol,diisopropyl phenol, and triisopropyl phenol. Preferred nonionicsurfactants are the TERGITOL 15-S-40 and TERGITOL NP-40 surfactantsavailable from Union Carbide. TERGITOL 15-S-40 surfactant (CAS#68131-40-8) is a reaction product of a mixture of 11-15 carbon, linearsecondary alcohols and ethylene oxide. TERGITOL NP-40 surfactant is thereaction product of a nonylphenol and about 40 moles of ethylene oxide.Another preferred nonionic surfactant is SURFYNOL 485 surfactantavailable from Air Products.

Anionic surfactants which may be used in the invention includesurfactants such as alkali metal or ammonium salts of alkyl, aryl oralkylaryl sulfonates, sulfates, phosphates, and the like. These anionicsurfactants include, for example, sodium lauryl sulfate, sodiumoctylphenol glycolether sulfate, sodium dodecylbenzene sulfonate, sodiumlauryldiglycol sulfate, and ammonium tritertiarybutyl phenol and penta-and octa-glycol sulfonates, sulfosuccinate salts such as disodiumethoxylated nonylphenol half ester of sulfosuccinic acid, disodiumn-octyldecyl sulfosuccinate, sodium dioctyl sulfosuccinate, and thelike. AEROSOL 18 surfactant, a 35% solution of N-octyldecylsulfosuccinimate in water and AEROSOL OT-75 surfactant, a 75% solutionof sodium dioctyl sulfosuccinate in water, from Cytech are preferredanionic surfactants.

Water-dispersible and water-soluble polymers may also be employed assurfactants/stabilizers in the water-based latexes of the invention.Examples of such polymeric stabilizers include water-dispersiblepolyesters as described in U.S. Pat. Nos. 4,946,932 and 4,939,233;water-dispersible polyurethanes as described in U.S. Pat. Nos. 4,927,876and 5,137,961; and alkali-soluble acrylic resins as described in U.S.Pat. No. 4,839,413. Cellulosics and polyvinyl alcohols may also be used.

The acetoacetoxy functionality in the SAAP may be present as freeacetoacetoxy groups or as derivatives of those groups such as, forexample, an enamine group or acetoacetamide group. Theacetoacetoxy-functional polymer may contain both free acetoacetoxygroups and acetoacetoxy derivatives. Surfactant-containingenamine-functional polymers according to the invention may be preparedby reacting a SAAP with ammonia or a primary or secondary amine.Typically, the reaction stoichiometry uses at least one molar equivalentof amino hydrogen (N--H) groups to acetoacetoxy groups.

Surfactant-containing enamine-functional polymers represent a preferredderivative of polymers of the invention. Enamine-functional polymers maybe used as the acetoacetoxy-functional polymer in the water-based latexof the invention. In water-based latexes, the enamine functionalityserves to further stabilize the acetoacetoxy-groups and protect themfrom hydrolysis. Enamine-functional polymers have been described inMoszner et al., Polymer Bulletin 32, 419-426 (1994); European patentApplication No. 0 492 847 A2; U.S. Pat. No. 5,296,530; and U.S. Pat. No.5,484,849. These documents are incorporated here by reference.

Enamine-functional polymers may be prepared by reacting a polymer havingacetoacetoxy groups with ammonia or a primary or secondary amine. Theprimary or secondary amine may be a monoamine compound or a polyaminecompound. Preferred amines include, for example, triaminononane, H₂N(CH₂)₃ CH(CH₂ NH₂)(CH₂)₄ NH₂ (CAS Registry No. 1572-55-0), availablefrom Monsanto; 2-amino-2-methyl-1-propanol available as AMP-95 productfrom Angus Chemical Company, Buffalo Grove, Ill.; or, as describedbelow, polyethylenimine, (PEI).

The preparation of enamine-functional vinyl polymers having pendantenamine groups is described in U.S. Pat. No. 5,484,849. Typically, thereaction stoichiometry uses at least one molar equivalent of aminohydrogen (N--H) groups to acetoacetoxy groups. Though the reaction israpid, an equilibrium exists between the enamine product and theacetoacetoxy/N--H reactants. The rate of enamine formation increaseswith temperature. Due to the equilibrium, however, an enamine-functionalpolymer may have both enamine and acetoacetoxy groups.

Enamine-functional polymers or copolymers may also be prepared bypolymerization of enamine-functional monomers. This method ofpreparation is described Moszner et al., Polymer Bulletin 32, 419-426(1994). Enamine-functional polymers also having allyl functionalitiesare described in U.S. Pat. No. 5,539,073 which is incorporated here byreference. Using these methods, an enamine-functional monomer may besubstituted for an acetoacetoxy-functional monomer of formula (1) toprepare surfactant-containing polymers of the invention.

To form a PPAE, a SAAP is reacted with a poly(alkylenimine). In general,a poly(alkylenimine) contains primary, secondary, and tertiary aminegroups. At least a portion of the primary and secondary amine groups ofthe poly(alkylenimine) react with the pendant acetoacetoxy groups on theSAAP to form enamine linkages yielding a crosslinked polymeric(polyamino)enamine or PPAE.

Poly(alkylenimines), particularly poly(ethylenimine), are known toflocculate latexes, and are actually sold for that purpose. In contrast,the PPAE of the present invention, does not flocculate, but provides astable, waterborne polymer composition. As shown in the examples below,adding a poly(alklyenimine) to a waterborne SAAP composition yields astable waterborne PPAE composition, without flocculation.Advantageously, the PPAE affords --NH functionalities which increaseadhesiveness and crosslinking ability of a coating formulationcontaining the PPAE.

A poly(alkylenimine) for use in the invention may have a weight averagemolecular weight of about 400 to about 750,000. The poly(alkylenimine)is preferably a poly(ethylenimine) (PEI) and more preferably PEI havinga weight average molecular weight of about 800 to about 25,000. Such PEIcompounds are commercially available from many sources and includePOLYMIN poly(ethylenimine) and LUPASOL poly(ethylenimine) available fromBASF Corporation. BASF polyethylenimine product literature reports theratio of primary:secondary:tertiary amine groups to be about 1:2:1. Apreferred PEI, LUPASOL G35 poly(ethylenimine), has a molecular wight of2,000 and a ratio of primary:secondary:tertiary amine groups of about1.5:1.4:1.

The reaction to form the PPAE may be accomplished by adding, withstirring, the appropriate poly(alkylenimine) to an emulsion of the SAAP.Sufficient poly(alkylenimine) should be used to achieve a molar ratio ofamino hydrogen (N--H) groups to acetoacetoxy groups of about 0.1 toabout 35, preferably a molar ratio from about 0.5 to about 20, and morepreferably, from about 1 to about 5. The amount of poly(alkylenimine)added to the polymer having pendant acetoacetoxy groups may range fromabout 1 phr (grams dry weight poly(alkylenimine) to 100 grams dry weightresin) to about 30 phr and preferably from about 7 phr to about 25 phr.A water-based solution of the poly(alkylenimine) is preferably combinedwith a SAAP emulsion over about 15-30 minutes at ambient temperature.When preparing the PPAE in a single reaction vessel, the reactionmixture containing the SAAP may need to be cooled before adding thepoly(alkylenimine).

In a water-based composition of the invention, theacetoacetoxy-functional, or enamine-functional polymers, (preferably aPPAE) may be present from about 5 to about 60 weight percent solids,based on the polymer's dry resin weight. More preferably, from about 25to about 55 weight percent of the water-based composition. The examplesbelow illustrate the polymer preparation and water-based compositions ofthe invention.

Latexes or other water-based compositions containing small particle sizepolymers, those ranging from about 25 to about 100 nm and morepreferably from about 45 to about 85 nm, represent one preferredembodiment of the invention. Advantageously, latex compositionscontaining these small particle enamine-functional polymers have a highsolids content, preferably about 25 to about 55, and more preferably,about 35 to about 55, percent solids, as well as low viscosity,preferably about 10 to about 1000 cps, and more preferably about 10 toabout 200 cps. The reactions used to prepare the polymers andcorresponding latexes of the invention produce low levels of coagulum.

FIG. 1 depicts the relationship between polymer particle size, percentsolids, and viscosity of a latex of the invention. As FIG. 1 shows, evenwith a particle size of nearly 60 nm and a 50% solids level, the latexviscosity is still less than 200 cps. Achieving this relationshipbetween particle size, solids content, and latex viscosity represents aparticular advantage of the invention. Accordingly, the inventionprovides waterborne polymer compositions which are stable, have highsolids content, but low viscosity. Advantageously, the polymer particleswithin the composition may be present as essentially monodispersedparticles. Such compositions are particularly well-suited for coatingformulations.

The pH of a waterborne polymer composition of the invention may beadjusted and/or buffered using, for example, buffers such as sodiumbicarbonate, ammonium bicarbonate, ammonium dihydrogenphosphate, anammonium poly(meth)acrylate, or a mixture of such buffers. The buffer,such as ammonium bicarbonate, may generally be added to the waterbornepolymer composition to adjust and/or buffer the pH of the composition.Waterborne polymer compositions having pH values in the range of about7.0 to 9.2, preferably 8.4 to 9.2, may be achieved using ammoniumbuffers. Buffered compositions of the invention are particularly usefulin coating formulations.

Advantageously, the enamine-functional polymers of the invention mayused to prepare stable cationic latexes having an acidic pH from ananionic stabilized latex without precipitation or coagulation of thelatex. Typically, a latex of the invention containing anenamine-functional polymer, such as a PPAE, has a pH of about 10 orabove. Adding a Bronsted acid to such a latex lowers the pH and belowneutral pH forms a stable cationic latex. A wide range pH values may beachieved, even pH values as low as 0.5. The acid is generally added to acooled latex. Any Bronsted acid may be used. For example, mineral acidssuch as sulfuric acid, phosphoric acid, hydrochloric acid, etc., andorganic acids such as p-toluene sulfuric acid, acetic acid, etc. may beused. Cationic latexes such as these are particularly useful in coatingcompostions for hard to adhere to substrates (for example rusty metalsurfaces). Exemplary coating compositions include laminate coatings,inks, textile coatings, coatings for plastic and primer coatings.

A waterborne polymer composition of the invention may also contain otheradditives known in those compositions and may use other emulsionpolymerization methodology. U.S. Pat. No. 5,371,148 describes suchadditives and is incorporated here by reference.

The polymers and waterborne polymer compositions of the invention areuseful in a variety of coating formulations such as metal coatings, woodcoatings, plastic coatings, textile coatings, cementitious coatings,paper coatings, inks, and adhesives. Examples of such coatingformulations adapted for particular uses include, but are not limitedto, corrosion inhibitors, architectural coatings, concrete coatings,maintenance coatings, latex paints, industrial coatings, automotivecoatings, textile back coatings, laminating inks and surface printinginks. Accordingly, the present invention relates to such coatingformulations containing a waterborne polymer composition of theinvention, preferably a water-based latex. The polymers and waterbornepolymer compositions of the invention may be incorporated in thosecoating formulations in the same manner as known polymer latexes andused with the conventional components and or additives of suchcompositions. The coating formulations may be clear or pigmented. Withtheir crosslinking ability, adhesion properties, and resistanceproperties, the water-based latexes of the invention impart new and/orimproved properties to the various coating formulations.

Upon formulation, a coating formulation containing a polymer orwaterborne polymer composition of the invention may then be applied to avariety of surfaces, substrates, or articles, e.g., paper, plastic,steel, aluminum, wood, gypsum board, concrete, brick, masonry, orgalvanized sheeting (either primed or unprimed). The type of surface,substrate, or article to be coated generally determines the type ofcoating formulation used. The coating formulation may be applied usingmeans known in the art. For example, a coating formulation may beapplied by spraying or by coating a substrate. In general, the coatingmay be dried by heating but preferably is allowed to air dry.Advantageously, a coating employing a polymer of the invention may bethermally or ambiently cured. As a further aspect, the present inventionrelates to a shaped or formed article which has been coated with acoating formulations of the present invention.

A coating formulation according to the invention may comprise a polymeror waterborne polymer composition of the invention, water, a solvent, apigment (organic or inorganic) and/or other additives and fillers knownin the art.

For example, a latex paint composition of the invention may comprise awaterborne polymer composition of the invention, a pigment and one ormore additives or fillers used in latex paints. Such additives orfillers include, but are not limited to, leveling, rheology, and flowcontrol agents such as silicones, fluorocarbons, urethanes, orcellulosics; extenders; curing agents such as multifunctionalisocyanates, multifunctional carbonates, multifunctional epoxides, ormultifunctional acrylates; reactive coalescing aids such as thosedescribed in U.S. Pat. No. 5,349,026; flatting agents; pigment wettingand dispersing agents and surfactants; ultraviolet (UV) absorbers; UVlight stabilizers; tinting pigments; extenders; defoaming andantifoaming agents; anti-settling, anti-sag and bodying agents;anti-skinning agents; anti-flooding and anti-floating agents; fungicidesand mildewcides; corrosion inhibitors; thickening agents; plasticizers;reactive plasticizers; drying agents; catalysts; crosslinking agents; orcoalescing agents. Specific examples of such additives can be found inRaw Materials Index, published by the National Paint & CoatingsAssociation, 1500 Rhode Island Avenue, NW, Washington, D.C. 20005.

In addition to those uses discussed above, the preferred PPAE polymer orwaterborne PPAE polymer composition of the invention may be used in manyof the same industries and applications where poly(alkylenimines) suchas PEI are now used. For example, a PPAE of the invention may be used asan adhesion promoter for binding proteins and enzymes to inertsubstrates, a shampoo additive to improve hair substantivity, as a dyefixative for textiles, a pigment dispersion for coatings, or aflocculant in water treatment.

A polymer or waterborne polymer composition of the invention can beutilized alone or in conjunction with other waterborne polymers. Suchpolymers include, but are not limited to, water dispersible polymerssuch as polyesters, polyester-amides, cellulose esters, alkyds,polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers,polymers having pendant allyl groups such as described in U.S. Pat. No.5,539,073, styrene-butadiene polymers, vinylacetate-ethylene copolymers,and the like.

Used in combination with certain other water-dispersible polymers, thePPAE polymers of the invention bring a unique advantage to the finalcomposition, in addition to their crosslinking ability, adhesionproperties, and resistance properties. The PPAE has the ability toscavenge, via a Michael Reaction, α,β-unsaturated carbonyl-containingmonomer or α,β-unsaturated electron withdrawing group-containing monomerremaining in the polymer latex. In other words, the PPAE scavengesresidual monomers or contaminants such as ketones, aldehydes,α,β-unsaturated acids, α,β-unsaturated esters, α,β-unsaturated amides,and α,β-unsaturated nitrites. Removing these monomers can, not onlyeliminate the odors associated with them, but also improve health andsafety when using the composition.

The following examples are intended to illustrate, not limit, theinvention. The examples and various coating formulations of theinvention use one or more of the following materials:

LUPASOL G35 poly(ethylenimine), 2,000 MW, sold by BASF as a 50% solutionin water.

TAMOL 1124 dispersant sold by Rohm & Haas Company.

RHOPLEX RM-2020 associative thickener sold by Rohm & Haas Company.

FOAMASTER AP and FOAMASTER VF defoamers sold by Henkel.

TI-PURE R-900 titanium dioxide pigment sold by DuPont.

TRITON CF-b10 surfactant sold by Union Carbide.

SURFYNOL 104 and 104DPM products (50% Solids), sold by Air Products andChemicals, Inc., Allentown, Pa.

DOWICIL 75 preservative, sold by Dow Chemical Company, Midland, Mich.

OMYACARB UF, a calcium carbonate extender, sold by Omya Inc., Proctor,Vt.

EASTMAN EB and EASTMAN DB solvents, sold by Eastman Chemical Company,Kingsport, Tenn.

TAFIGEL PUR 45 thickener, sold by King Industries, Norwalk, Conn.

RHEOVIS CR2 thickener, sold by Allied Colloids, Suffolk, Va.

t-butylhydroperoxide was used as a 70% solution in water.

TEXANOL coalescing solvent sold by Eastman Chemical Company, Kingsport,Tenn.

The following methods were used to evaluate the coatings and filmsprepared according to the invention.

Constant Temperature and Humidity Room:

Films were prepared and film measurements were conducted in a constanttemperature and humidity (CTH) room at ASTM standard conditions forlaboratory testing of 73.5±3.5° F. (23±2° C.) and 50±5% relativehumidity.

Film Gel Fraction (FGF) and Film Swell Ratio (FSR):

Film gel fraction (FGF) is obtained by determining the insoluble weightfraction of polymer in a dry film sample. Film swell ratio (FSR) isobtained by determining the ratio of the insoluble polymer weightfraction swollen in the selected solvent (by weight) to dry weight ofthe insoluble weight fraction in a dry film sample. Average values aredetermined from quadruplicate measurements with acetone as the solvent.

The procedure used was as follows: for each sample determination, a4"×4"325-mesh steel screen and a metal weighing boat are baked in avacuum oven at 120° C. for 90 minutes, cooled 30 minutes over P₂ O₅ andweighed (W1 and W2, respectively). After the latex film is dried therequired number of days under constant temperature and humidity or bakedin the oven at the specified time and temperature, a piece of the filmis cut, weighed (W3), placed in the aluminum pan, and put aside. Anotherfilm sample is cut, weighed (W4), and placed in a screw cap jar withexcess solvent on a shaker bath for 16 hours at constant temperature.The film gel is recovered by pouring the solution plus wet solids fromthe jar through the screen and then weighing the screen plus retainedwet solids (W5). At this point, the screen plus solids and the filmsample in the aluminum boat are dried in a forced air oven at 80° C.overnight and then in a vacuum oven at 120° C. for 3 hours and cooledfor 30 minutes in a desiccator over P₂ O₅. The samples are weighed andthe vacuum portion of the baking procedure is repeated untilreproducible weights are obtained for the screen plus dry solids (W6)and the film sample in the aluminum boat (W7).

Calculations were made by the equations shown below:

    FGF=(W6-W1)/[(W4)*[(W7-W2)/W3]]

    FSR=(W5-W1)/(W6-W1)

Tensile:

Tensile tests are performed in the CTH room on a on a United TensileTester Model STM-1-PC, which is a constant rate of elongation machine.Film samples are obtained by casting the sample on release paper with a7 mil bird bar, drying the film for the desired time at the statedconditions, and cutting a dogbone-shaped thin-film sample with a 1" widedie. The film is measured for film thickness, mounted in the tensiletester grips and tested at a crosshead speed of 1"/minute using a 5lb-force load cell. Ten samples are run and the five samples with thegreater breaking stress are averaged for all tensile values reportedaccording to ASTM D2370. Tensile values were calculated using Datumsoftware from United Testing Systems, Inc., Flint, Mich.

Glass Transition:

Onset and midpoint temperatures were determined on film samples using adifferential scanning calorimeter (DSC) in a nitrogen atmosphere at aheating rate of 20° C./min. values quoted are from the reheat curve.

Color:

Seven mil wet emulsion films are cast on polyester sheets. The coatedpolyester sheet and an uncoated control polyester sheet are allowed todry under the specified conditions. Color is measured of both the clearemulsion film and the control panel placed on top of a white controlpanel using a colorimeter in the L,a,b mode.

Paint Viscosity:

Paint viscosity (in Krebs Units) was measured after 24 hours using aKrebs-Stormer viscometer.

Gloss:

Gloss was measured on 6 mil (wet) thick films cast on Leneta 2B opacitypaper after 24 hours using a micro-tri-glossmeter by BYK-Gardneraccording to ASTM method D 523 Test Method for Specular Gloss.

Blocking Resistance:

Blocking resistance was determined using 6 mil (wet) films on Leneta 2Bopacity paper according to ASTM 4946 Test Method for Blocking Resistanceof Architectural Paints using 1 psi pressure after film dried todesignated times. Heated block resistance was determined in a forced airoven at 120° F. with the painted surfaces face-to-face under 1 psipressure for 30 minutes. The tests were numerically rated where a ratingof 1 represents 100% pass where painted surfaces lift apart with nonoise, a rating of 2 represents noise when painted surfaces areseparated but no film degradation occurs, a rating of 3 represents somedestruction of the painted surfaces when the two surfaces are separatedand a rating of 4 represents 100% fail where the painted surfaces flowcompletely together and complete destruction of the films occurs uponseparation.

Print Resistance:

Print resistance was determined using 6 mil (wet) films on Leneta 2Bopacity paper according to ASTM D 2064-91 Test Method for PrintResistance of Architectural Paints using a 4 psi pressure placed on topof a #6 black rubber stopper which was placed on four layers ofcheesecloth after film dried to designated times. Heated printresistance was determined in a forced air oven at 120° F. with foldedcheesecloth (as above) under 4 psi pressure for 30 minutes. The testswere numerically rated where a rating of 1 represents 100% pass with nodemarcation (cloth lifts off with no print left behind), a rating of 2represents demarcations (some impression is observed), a rating of 3represents 100% fail (the cheesecloth impregnates the film).

Scrub Resistance:

Scrub resistance was determined following ASTM D2486 Test Method forscrub resistance of architectural coatings. The coating is applied at 7mil wet on Scrub Test Charts Form P 121-10N and allowed to dry for thespecified period of time. The panel is placed in a Gardco Scrub Machine,Model D-10V, 10 g of Standardized Scrub Medium (abrasive type) for ASTMD2486 and D3450 is placed on the scrub brush, the panel is wet with 5 mlDI water, the test machine counter is zeroed, and the test is run at themaximum test speed on the machine. After each 400 cycles before failure,the brush is removed and 10 more g of scrub medium is added evenly onthe bristles, the brush is replaced, 5 ml of DI water is placed on thepanel and the test is continued. The test is stopped at 1000 cycles orfailure, whichever comes first. Failure is defined as the number ofcycles to remove the paint film fully in one continuous line across thewidth of the shim.

Wet Adhesion Test:

This procedure tests the coatings adhesion to an aged, alkyd substrateunder wet, scrubbing conditions. This procedure is described in "VYNATE™(Union Carbide Chemicals and Plastics Corporation)--Vinyl EmulsionVehicles for Semigloss Interior Architectural Coatings", M. J. Collins,et al., presented at the 19th Annual "Water-Borne High-Solids and PowderCoating Symposium", Feb. 26-28, 1992, New Orleans, La, USA.

A ten-mil drawdown of a commercial gloss alkyd paint is made on a"Leneta" scrub panel (adhesion varies from alkyd to alkyd--a GliddenIndustrial Enamel was used.) The alkyd film is allowed to age one weekat ambient conditions, then baked at 110° F. for 24 hours, and then agedat least one more week at ambient conditions. A seven-mil drawdown ofthe test paint is then made over the aged alkyd and allowed to air drythree days. (In order to differentiate between samples that pass thistest, dry times may be shortened. Seven days is a common period, andoccasionally 5 hours dry time is used. Constant temperature/humidityconditions, 72° F./50%, are normally used for drying.) The test paint isthen cross-hatched with a razor and submerged in water for 30 minutes.The paint film is inspected for blistering and scratched with thefingernail to gauge the adhesion. While still wet, the panel is placedon a "Gardner" scrub machine. Ten ml of five percent "LAVA™" soap slurryare added to the film, and the nylon scrub brush (WG 2000NB) is passedover the scored paint film area. Water is added as needed to keep thepaint film wet (flooded). The number of brushing cycles for initial peeland ten percent peel are noted. The number of cycles for completeremoval of the film is often noted also.

EXAMPLE 1 Preparation of a Large Particle Size, Core/ShellEnamine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 640 g of water, 4.05 g of TREM LF-40,1.93 g of TERGITOL NP-40(70%), 7.3 g of sodium carbonate, 44.24 g ofmethyl methacrylate, 8.26 g of styrene, 57.09 g of 2-ethylhexylacrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogenpurge was begun, then the contents of the reactor brought up to 80° C.at 400 rpm. After reaching 80° C., an initiator charge composed of 7.70g of sodium persulfate dissolved in 43.6 g of water was added to thereactor. An emulsion feed composed of 355 g of water, 11.7 g of TREMLF-40, 10.21 g of TERGITOL NP-40 (70%), 271.78 g of methyl methacrylate,50.72 g of styrene, 350.63 g of 2-ethylhexyl acrylate, and 1.55 g oftrimethylolpropane triacrylate was begun at 8.38 g/min. Five minutesafter the first emulsion feed was begun, an initiator solution composedof 4.36 g of sodium persulfate dissolved in 112 g of water was fed at0.466 g/min. After the first emulsion feed was completed, a secondemulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 gof TERGITOL NP-40 (70%), 180.88 g of styrene, 90.0 g of 2-ethylhexylacrylate, 143.92 g of acetoacetoxyethyl methacrylate, and 1.68 g of thesodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at8.38 g/min. Five minutes after the last feed, an initiator solution of1.34 g of t-butyl hydroperoxide, and 1.34 g of sodium formaldehydesulfoxylate dissolved in 40.2 g of water was charged and heatingcontinued for 30 minutes. The emulsion was cooled, and 45 g of ammoniumhydroxide (28%) were pumped in over 15 minutes. The latex was thenfiltered through 100 mesh wire screen. Solids level, 46.0; pH, 8.4;amount of dried material (100 mesh screen), 11.6 g; particle size (Dw),236 nm, ZETA potential, -47.1 mv, latex gel fraction/swell ratio 42/9.6.Infrared analysis of clear films cast over ZnSe showed an absorption at1565 cm⁻¹ which represents an enamine moiety.

EXAMPLE 2 Preparation of a Large Particle Size, Core/ShellPEI-Containing Waterborne Polymer

The procedure for the preparation of this latex was similar to the latexpreparation described in Example 1 except that 247.35 g ofpoly(ethylenimine) (50% in water) was added in place of the ammoniumhydroxide solution. Mole ratio of N--H group to acetoacetoxy group was4.27. The latex was then filtered through 100 mesh wire screen. Solidslevel, 46.8; pH, 10; amount of dried material (100 mesh screen), 3.28 g;particle size (Dw), 225 nm, ZETA potential, -23.7 mv (pH=11.7), latexgel fraction/swell ratio 75/6.1. Infrared analysis of clear films castover ZnSe showed an absorption at 1653 cm⁻¹ and 1565 cm⁻¹ and adisappearance of the absorbencies at 1631 cm⁻¹ and 1655 cm⁻¹ afteraddition of the poly(ethylenimine). After reacting thepoly(ethylenimine) with the pendant acetoacetoxy group, the latex wascentrifuged and the water phase analyzed. Elemental analysis of thewater phase showed that at most 2% of the poly(ethylenimine) remained inthe water phase.

EXAMPLE 3 Preparation of a Large Particle Size, Core/ShellPEI-Containing Waterborne Polymer

The procedure for the preparation of this latex was similar to the latexpreparation described in Example 1 except that 316.86 g ofpoly(ethylenimine) (50% in water) was added in place of the amrnoniumhydroxide solution. Mole ratio of N--H group to acetoacetoxy group was5.47. The latex was then filtered through 100 mesh wire screen. Solidslevel, 46.5; pH, 10; amount of dried material (100 mesh screen), 4.11 g;particle size (Dw), 225 nm, latex gel fraction/swell ratio 76/5.7.Infrared analysis of clear films cast over ZnSe showed an absorption at1653 cm⁻¹ and 1565 cm⁻¹ and a disappearance of the absorbencies at 1631cm⁻¹ and 1655 cm⁻¹ after addition of the poly(ethylenimine). Afterreacting the poly(ethylenimine) with the pendant acetoacetoxy group, thelatex was centrifuged and the water phase analyzed. Elemental analysisof the water phase showed that at most 2% of the poly(ethylenimine)remained in the water phase.

EXAMPLE 4 Preparation of a Small Particle Size, Core/ShellEnamine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 1100 g of water, 49.0 g of HITENOLHS-20, 8.05 g of TERGITOL NP-40(70%), 7.3 g of sodium carbonate, 44.24 gof methyl methacrylate, 8.26 g of styrene, 57.09 g of 2-ethylhexylacrylate, and 0.252 g of trimethylolpropane triacrylate. A nitrogenpurge was begun, then the contents of the reactor brought up to 80° C.at 400 rpm. After reaching 80° C., an initiator charge composed of 7.70g of sodium persulfate dissolved in 43.6 g of water was added to thereactor. An emulsion feed composed of 273.5 g of water, 19.65 g ofAEROSOL 18, 20.19 g of TERGITOL NP-40 (70%), 271.78 g of methylmethacrylate, 50.72 g of styrene, 350.63 g of 2-ethylhexyl acrylate, and1.55 g of trimethylolpropane triacrylate was begun at 8.38 g/min. Fiveminutes after the first emulsion feed was begun, an initiator solutioncomposed of 4.36 g of sodium persulfate dissolved in 112 g of water wasfed at 0.466 g/min. After the first emulsion feed was completed, asecond emulsion feed composed of 147 g of water, 12.15 g of AEROSOL 18,12.5 g of TERGITOL NP-40 (70%), 180.88 g of styrene, 90.0 g of2-ethylhexyl acrylate, 143.92 g of acetoacetoxyethyl methacrylate, and1.68 g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% inwater) was fed at 8.38 g/min. Five minutes after the last feed, aninitiator solution of 1.34 g of t-butyl hydroperoxide, and 1.34 g ofsodium formaldehyde sulfoxylate dissolved in 40.2 g of water was chargedand heating continued for 30 minutes. The emulsion was cooled, and 45 gof ammonium hydroxide (28%) were pumped in over 15 minutes. The latexwas then filtered through 100 mesh wire screen. Solids level, 41.0;amount of dried material (100 mesh screen), 4.8 g; particle size (Dw),65 nm, latex gel fraction/swell ratio 57/11.6. Infrared analysis ofclear films cast over ZnSe showed an absorption at 1565 cm⁻¹ whichrepresents an enamine moiety.

EXAMPLE 5 Preparation of a Small Particle Size, Core/ShellPEI-Containing Waterborne Polymer

The procedure for the preparation of this latex was similar to the latexpreparation described in Example 1 except that 247.35 g ofpoly(ethylenimine) (50% in water) was added in place of the ammoniumhydroxide solution. Mole ratio of N-H group to acetoacetoxy group was4.27. The latex was then filtered through 100 mesh wire screen. Solidslevel, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g;particle size (Dw), 58 nm, latex gel fraction/swell ratio 62/5.6.Infrared analysis of clear films cast over ZnSe showed an absorption at1653 cm⁻¹ and 1565 cm⁻¹ and a disappearance of the absorbencies at 1631cm⁻¹ and 1655 cm⁻¹ after addition of the poly(ethylenimine). Afterreacting the poly(ethylenimine) with the pendant acetoacetoxy group, thelatex was centrifuged and the water phase analyzed. Elemental analysisof the water phase showed that at most 2% of the poly(ethylenimine)remained in the water phase.

EXAMPLE 6 Preparation of a Small Particle Size, Core/ShellPEI-Containing Waterborne Polymer

The procedure for the preparation of this latex was similar to the latexpreparation described in Example 1 except that 314.45 g ofpoly(ethylenimine) (50% in water) was added in place of the ammoniumhydroxide solution. Mole ratio of N--H group to acetoacetoxy group was4.27. The latex was then filtered through 100 mesh wire screen. Solidslevel, 41.6; pH, 10; amount of dried material (100 mesh screen), 3.03 g;particle size (Dw), 70 nm, latex gel fraction/swell ratio 61/6.5.Infrared analysis of clear films cast over ZnSe showed an absorption at1653 cm⁻¹ and 1565 cm⁻¹ and a disappearance of the absorbencies at 1631cm⁻¹ and 1655 cm⁻¹ after addition of the poly(ethylenimine). Afterreacting the poly(ethylenimine) with the pendant acetoacetoxy group, thelatex was centrifuged and the water phase analyzed. Elemental analysisof the water phase showed that at most 2% of the poly(ethylenimine)remained in the water phase.

EXAMPLE 7 Preparation of a Large Particle Size, Core/ShellPEI-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 640 g of water, 4.05 g of TREM LF-40,1.93 g of TERGITOL NP-40(70%), 7.3 g of sodium carbonate, 55.23 g ofmethyl methacrylate, 4.03 g of styrene, 47.40 g of 2-ethylhexylacrylate, 20.15 g of acetoacetoxyethyl methacrylate, and 0.336 g oftrimethylolpropane triacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator charge composed of 7.70 g of sodium persulfatedissolved in 43.6 g of water was added to the reactor. An emulsion feedcomposed of 355 g of water, 11.7 g of TREM LF-40, 10.21 g of TERGITOLNP-40 (70%), 271.78 g of methyl methacrylate, 50.72 g of styrene, 350.63g of 2-ethylhexyl acrylate, and 1.55 g of trimethylolpropane triacrylatewas begun at 8.38 g/min. Five minutes after the first emulsion feed wasbegun, an initiator solution composed of 4.36 g of sodium persulfatedissolved in 112 g of water was fed at 0.5.36 g/min. After the firstemulsion feed was completed, a second emulsion feed composed of 171 g ofwater, 12.79 g of AEROSOL 18, 5.09 g of TERGITOL NP-40 (70%), 211.03 gof styrene, 80.0 g of 2-ethylhexyl acrylate, 123.77 g ofacetoacetoxyethyl methacrylate, and 1.68 g of the sodium2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 8.38g/min. Five minutes after the last feed, an initiator solution of 1.34 gof t-butyl hydroperoxide, and 1.34 g of sodium formaldehyde sulfoxylatedissolved in 40.2 g of water was charged and heating continued for 30minutes. The emulsion was cooled, and filtered through 100 mesh wirescreen. Solids level, 46.64; pH, 8.2; amount of dried material (100 meshscreen), 24.65 g; Particle Size, (Electron Microscopy), 450 nm. To 2500g of this latex were added over 15 minutes 115 g of poly(ethylenimine)(50%). Solids, 46.6%; pH, 10.4; Particle Size (Electron Microscopy), 450nm. Infrared analysis of clear films cast over ZnSe showed an absorptionat 1653 cm⁻¹ and 1565 cm⁻¹ and a disappearance of the absorbencies at1631 cm⁻¹ and 1655 cm⁻¹ after addition of the poly(ethylenimine).

EXAMPLE 8 Preparation of a Small Particle Size, UnstructuredEnamine-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 290 g of water, 15.52 g of HITENOLHS-20, 2.55 g of TERGITOL NP-40 (70%), 3.5 g of sodium carbonate, 8.10 gof methyl methacrylate, 5.38 g of 2-ethylhexyl acrylate, and 4.43 g ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator charge composed of 2.30 g of sodium persulfatedissolved in 13.0 g of water was added to the reactor. An emulsion feedcomposed of 120 g of water, 6.55 g of AEROSOL 18, 10.22 g of TERGITOLNP-40 (70%), 153.66 g of methyl methacrylate, 102.03 g of 2-ethylhexylacrylate, and 84.21 g of acetoacetoxyethyl methacrylate was begun at8.38 g/min. Five minutes after the first emulsion feed was begun, aninitiator solution composed of 1.3 g of sodium persulfate dissolved in33.5 g of water was fed at 0.536 g/min. Five minutes after the monomerfeed, an initiator solution of 0.40 g of t-butyl hydroperoxide, and 0.40g of sodium formaldehyde sulfoxylate dissolved in 12 g of water wascharged and heating continued for 30 minutes. The emulsion was cooled,and 27.7 g of ammonium hydroxide (28%) were pumped in over 15 minutes.The latex was then filtered through 100 mesh wire screen. Solids level,43.3; amount of dried material (100 mesh screen), 0.12 g; particle size(Dn), 50 um. Infrared analysis of clear films cast over ZnSe showed anabsorption at 1568 cm⁻¹ which represents an enamine moiety.

EXAMPLE 9 Preparation of a Small Particle Size, UnstructuredPEI-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 232 g of water, 12.42 g of HITENOLHS-20, 2.02 g of TERGITOL NP-40(70%), 2.8 g of sodium carbonate, 4.15 gof methyl methacrylate, 5.38 g of 2-ethylhexyl acrylate, and 4.33 g ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator charge composed of 1.84 g of sodium persulfatedissolved in 10.4 g of water was added to the reactor. An emulsion feedcomposed of 96 g of water, 5.24 g of AEROSOL 18, 8.18 g of TERGITOLNP-40 (70%), 78.90 g of methyl methacrylate, 110.82 g of 2-ethylhexylacrylate, and 82.36 g of acetoacetoxyethyl methacrylate was begun at8.38 g/min. Five minutes after the first emulsion feed was begun, aninitial solution composed of 1.04 g dissolved in 26.8 g of water was fedat 0.536 g/min. Five minutes after the monomer feed, an initiatorsolution of 0.32 g of t-butyl hydroperoxide, and 0.32 g of sodiumformaldehyde sulfoxylate dissolved in 9.6 g of water was charged andheating continued for 30 minutes. The emulsion was cooled to 30° C., and139.58 g of poly(ethylenimine) (50% in water) were pumped in over 15minutes. Mole ratio of N--H group to acetoacetoxy group was 4.00. Thelatex was then filtered through 100 mesh wire screen. Solids level,42.8; pH, 10; amount of dried material (Recoverable Solids, 100 meshscreen), 0.10 g; particle size (Dw), 54 nm. Infrared analysis of clearfilms cast over ZnSe showed an absorption at 1653 cm⁻¹ and 1592 cm⁻¹ anda disappearance of the absorbencies at 1631 cm⁻¹ and 1655 cm⁻¹ afteraddition of the poly(ethylenimine). After reacting thepoly(ethylenimine) with the pendant acetoacetoxy group, the latex wascentrifuged and the water phase analyzed. Elemental analysis of thewater phase showed that at most 1% of the poly(ethylenimine) remained inthe water phase.

EXAMPLE 10 Preparation of a Large Particle Size, Core/Shell Allyl- andAcetoacetoxy-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 529.6 g of water, 2.87 g of TREM LF-40,1.36 g of TERGITOL NP-40 (70%), 7.1 g of sodium carbonate, 5.01 g ofmethyl methacrylate, 28.95 g of styrene, 17.54 g of methyl methacrylate,33.78 g of 2-ethylhexyl acrylate, and 0.16 g of trimethylolpropanetriacrylate. A nitrogen purge was begun, then the contents of thereactor brought up to 80° C. at 400 rpm. After reaching 80° C., aninitiator solution composed of 5.28 g of sodium persulfate dissolved in20.88 g of water was added to the reactor. An initiator solutioncomposed of 3.56 g of sodium persulfate dissolved in 53.77 g of waterwas fed into the reactor at 0.336 g/min. Ten minutes after the initiatorfeed was started, an emulsion feed composed of 192.6 g of water, 8.31 gof TREM LF-40, 7.25 g of TERGITOL NP-40 (70%), 107.72 g of methylmethacrylate, 177.89 g of styrene, 207.54 g of 2-ethylhexyl acrylate,and 0.98 g of trimethylolpropane triacrylate was begun at 5.25 g/min.After the first emulsion feed was completed, the lines were rinsed with160 g of water, and heating continued. After 25 minutes, a secondemulsion feed composed of 205 g of water, 15.73 g of AEROSOL 18, 6.12 gof TERGITOL NP-40 (70%), 251.8 g of styrene, 175.1 g of 2-ethylhexylacrylate, 94.94 g of acetoacetoxyethyl methacrylate, 47.92 g of allylmethacrylate, 23.99 g of dimethylaminoethyl methacrylate, and 4.79 g of2-ethylhexyl 3-mercaptopropionate was started at 8 g/minute. Ten minutesafter the feeds were completed, an initiator solution composed of 1.34 gof sodium formaldehyde sulfoxylate and 1.34 g of t-butylhydroperoxidedissolved in 40.2 g of water was fed into the reactor over 15 minutes.The latex was then filtered through 100 mesh wire screen. Solids level,47%; amount of dried material (100 mesh screen), 1.7 g.

EXAMPLE 11 Preparation of a Small Particle Size, Core/ShellAmine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 1100 g of water, 49 g of HITENOL HS-20,8.05 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 36.6 g ofmethyl methacrylate, 36.1 g of styrene, 36.2 g of 2-ethylhexyl acrylate,and 0.335 g of trimethylolpropane triacrylate. A nitrogen purge wasbegun, then the contents of the reactor brought up to 80° C. at 400 rpm.After reaching 80° C., an initiator solution composed of 7.05 g ofsodium persulfate dissolved in 43.55 g of water was added to thereactor. An initiator solution composed of 4.36 g of sodium persulfatedissolved in 112 g of water was started at 0.466 g/min. Thirty minutesafter the initiator feed was begun, an emulsion feed composed of 355 gof water, 19.65 g of AEROSOL 18, 20.19 g of TERGITOL NP-40 (70%), 224.84g of methyl methacrylate, 221.95 g of styrene, 224.4 g of 2-ethylhexylacrylate, and 2.06 g of trimethylolpropane triacrylate was begun at 5.24g/min. After the first emulsion feed was completed, a second emulsionfeed composed of 147 g of water, 12.15 g of AEROSOL 18, 12.48 g ofTERGITOL NP-40 (70%), 168.6 g of styrene, 80 g of 2-ethylhexyl acrylate,and 167.9 g cf acetoacetoxyethyl methacrylate was fed at 8.4 g/min. Tenminutes after the feeds were completed, an initiator solution composedof 1.34 g of sodium formaldehyde sulfoxylate and 1.34 g oft-butylhydroperoxide dissolved in 40.2 g of water was charged to thereactor and heating continued for 30 minutes. The emulsion was cooled toless than 35° C., and 283.84 g of polyethylenimine (50%) were pumped inover 15 minutes. The latex was then filtered through 100 mesh wirescreen. Solids level, 41.8; amount of dried material (100 mesh screen),0.60 g; pH, 10.5. Infrared analysis of clear films cast over ZnSe showedan absorption at 1565 cm-¹ which represents an enamine moiety.

EXAMPLE 12 Preparation of a Large Particle Size, UnstructuredAcetoacetoxy-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 294 g of water, 1.34 g of TREM LF-40,1.79 g of TERGITOL NP-40 (100%), 2.044 g of sodium carbonate, 9.67 g ofstyrene, 6.09 g of 2-ethylhexyl acrylate, and 0.01 g of sodium2-acrylamido-2-methylpropanesulfonate (50% in water). A nitrogen purgewas begun, then the contents of the reactor brought up to 80° C. at 400rpm. After reaching 80° C., an initiator solution composed of 2.3 g ofsodium persulfate dissolved in 13.0 g of water was added to the reactor.An initiator solution composed of 1.3 g of sodium persulfate dissolvedin 34 g of water was fed into the reactor at 0.16 g/min. Ten minutesafter the initiator feed was started, an emulsion feed composed of 120 gof water, 9.94 g of AEROSOL 18, 7.16 g of TERGITOL NP-40 (100%), 186.6 gof styrene, 115.63 g of 2-ethylhexyl acrylate, 40.81 g ofacetoacetoxyethyl methacrylate, and 0.52 g of sodium2-acrylamido-2-methylpropanesulfonate (50% in water) was fed into thereactor at 1.72 g/min. Five minutes after the feeds were completed, thenan initiator solution composed of 0.4 g of sodium persulfate and 0.4 gof sodium metabisulfite dissolved in 12 g of water was added to thereactor and heating continued for 30 minutes. The latex was thenfiltered through 100 mesh wire screen. Solids level, 42.6; amount ofdried material (100 mesh screen), 0.20 g; particle size (Dw), 153 nm; Tgof Polymer, 14° C.

EXAMPLE 13 Preparation of a Large Particle Size, UnstructuredAcetoacetoxy-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 351 g of water, 0.76 g of AEROSOL OT,5.11 g of TERGITOL NP-40 (100%), 2.05 g of sodium carbonate, 3.58 g ofstyrene, 11.63 g of 2-ethylhexyl acrylate, and 2.68 g of sodium2-acrylamido-2-methylpropanesulfonate (50% in water). A nitrogen purgewas begun, then the contents of the reactor brought up to 80° C. at 400rpm. After reaching 80° C., an initiator solution composed of 2.3 g ofsodium persulfate dissolved in 13.0 g of water was added to the reactor.An initiator solution composed of 1.3 g of sodium persulfate dissolvedin 34 g of water was fed into the reactor at 0.16 g/min. Ten minutesafter the initiator feed was started, a monomer feed composed of 4.10 gof AEROSOL OT (75%), 88.02 g of styrene, 221.06 g of 2-ethylhexylacrylate, 51.01 g of acetoacetoxyethyl methacrylate, and 0.26 g ofsodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed intothe reactor at 1.72 g/min. Five minutes after the feeds were completed,then an initiator solution composed of 0.4 g of sodium persulfate and0.4 g of sodium metabisulfite dissolved in 12 g of water was added tothe reactor and heating continued for 30 minutes. The latex was thenfiltered through 100 mesh wire screen. Solids level, 47.6; amount ofdried material (100 mesh screen), 0.10 g; particle size (Dw), 122 nm; Tgof Polymer, -28° C.

EXAMPLE 14 Preparation of a Large Particle Size, UnstructuredAcetoacetoxy-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 294 g of water, 1.34 g of TREM LF-40,1.79 g of TERGITOL NP-40 (100%), 2.044 g of sodium carbonate, 12.71 g ofstyrene, 3.84 g of isooctyl acrylate, and 0.014 g of sodium2-acrylamido-2-methylpropanesulfonate (50% in water). A nitrogen purgewas begun, then the contents of the reactor brought up to 80° C. at 400rpm. After reaching 80° C., an initiator solution composed of 2.3 g ofsodium persulfate dissolved in 13.0 g of water was added to the reactor.An initiator solution composed of 1.3 g of sodium persulfate dissolvedin 34 g of water was fed into the reactor at 0.16 g/min. Ten minutesafter the initiator feed was started, an emulsion feed composed of 120 gof water, 9.94 g of AEROSOL 18, 7.16 g of TERGITOL NP-40 (100%), 241.47g of styrene, 73.02 g of isooctyl acrylate, 25.61 g of acetoacetoxyethylmethacrylate, and 0.52 g of sodium 2-acrylamido-2-methylpropanesulfonate(50% in water) was fed into the reactor at 1.72 g/min. Five minutesafter the initiator solution feed was in, an initiator solution of 0.72g of sodium formaldehyde sulfoxylate and 1.03 g of t-butylhydroperoxidedissolved in 12 g of water was added to the reactor. The latex was thenfiltered through 100 mesh wire screen. Solids level, 43.8; amount ofdried material (100 mesh screen); 3.3 g; pH, 7.4; particle size (Dw),151 nm; Tg of Polymer, 16° C.

EXAMPLE 15 Preparation of a Large Particle Size, Core/ShellAmine-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 192 g of water, 1.22 g of TREM LF-40,0.79 g of TERGITOL NP-40 (70%), 2.4 g of sodium carbonate, 13.55 g ofmethyl methacrylate, 1.21 g of styrene, 17.24 g of 2-ethylhexylacrylate, 0.10 g of trimethylolpropane triacrylate, and 6.04 g ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator solution composed of 2.31 g of sodium persulfatedissolved in 13.06 g of water was added to the reactor. An initiatorsolution composed of 1.31 g of sodium persulfate dissolved in 34 g ofwater was started at 0.54 g/min. Thirty minutes after the initiator feedwas begun, an emulsion feed composed of 106 g of water, 3.51 g of TREMLF-40, 3.06 g of TERGITOL NP-40 (70%), 83.23 g of methyl methacrylate,7.44 g of styrene, 105.91 g of 2-ethylhexyl acrylate, and 0.619 g oftrimethylolpropane triacrylate was begun at 8.38 g/min. After the firstemulsion feed was completed, the feed lines were washed with 80 g ofwater, and the temperature held at 80° C. for 30 minutes. A secondemulsion feed composed of 53 g of water, 3.84 g of AEROSOL 18, 1.53 g ofTERGITOL NP-40 (70%), 63.31 g of styrene, 24.0 g of 2-ethylhexylacrylate, 37.13 g of acetoacetoxyethyl methacrylate, and 0.50 g of thesodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at8.38 g/min. Five minutes after the initiator solution feed was in, aninitiator solution of 0.40 g of sodium formaldehyde sulfoxylate and 0.40g of t-butylhydroperoxide dissolved in 12.1 g of water was added to thereactor. The emulsion was cooled to less than 35° C., and 69.51 g ofpolyethylenimine (50%) were pumped in over 15 minutes. The latex wasthen filtered through 100 mesh wire screen. Solids level, 46.6; amountof dried material (100 mesh screen), 0.15 g; particle size (Dw), 167 nm;Tg, 5° C.

EXAMPLE 16 Preparation of a Large Particle Size, Core/ShellAmine-Containing Waterborne Polymer

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 640 g of water, 4.05 g of TREM LF-40,1.93 g of TERGITOL NP-40 (70%), 8.0 g of sodium carbonate, 55.23 g ofmethyl methacrylate, 4.04 g of styrene, 47.4 g of 2-ethylhexyl acrylate,0.33 g of trimethylolpropane triacrylate, and 20.1 g ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator solution composed of 7.0 g of sodium persulfatedissolved in 43.6 g of water was added to the reactor. An initiatorsolution composed of 4.36 g of sodium persulfate dissolved in 122 g ofwater was started at 0.54 g/min. Thirty minutes after the initiator feedwas begun, an emulsion feed composed of 355 g of water, 11.7 g of TREMLF-40, 10.21 g of TERGITOL NP-40 (70%), 399.3 g of methyl methacrylate,24.78 g of styrene, 291.2 g of 2-ethylhexyl acrylate, and 2.06 g oftrimethylolpropane triacrylate was begun at 8.38 g/min. After the firstemulsion feed was completed, the feed lines were washed with 80 g ofwater, and the temperature held at 80° C. for 30 minutes. A secondemulsion feed composed of 171 g of water, 12.79 g of AEROSOL 18, 5.09 gof TERGITOL NP-40 (70%), 211 g of styrene, 80.0 g of 2-ethylhexylacrylate, 123.8 g of acetoacetoxyethyl methacrylate, and 1.68 g of thesodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at8.38 g/min. Five minutes after the initiator solution feed was in, aninitiator solution of 1.34 g of sodium formaldehyde sulfoxylate and 1.34g of t-butylhydroperoxide dissolved in 40.2 g of water was added to thereactor. The emulsion was cooled to less than 35° C., and 121 g ofpolyethylenimine (50%) were pumped in over 15 minutes. The latex wasthen filtered through 100 mesh wire screen. Solids level, 46.6; amountof dried material (100 mesh screen), 25 g; particle size (Dw), 450 nm;Tg, 14° C.; pH, 10.4

EXAMPLE 17 Preparation of a Large Particle Size, Core/Shell Allyl- andAcetoacetoxy-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 480 g of water, 1.30 g of HITENOL HS-20,1.08 g of TERGITOL 15-S-40 (100%), 5.84 g of sodium carbonate, 5.01 g ofmethyl methacrylate, 8.27 g of styrene, 9.63 g of 2-ethylhexyl acrylate,and 0.0689 g of trimethylolpropane triacrylate. A nitrogen purge wasbegun, then the contents of the reactor brought up to 80° C. at 400 rpm.After reaching 80° C., an initiator solution composed of 6.16 g ofsodium persulfate dissolved in 34.84 g of water was added to thereactor. An initiator solution composed of 3.48 g of sodium persulfatedissolved in 89.8 g of water was fed into the reactor at 0.336 g/min.Ten minutes after the initiator feed was started, an emulsion feedcomposed of 210.4 g of water, 2.75 g of AEROSOL OT, 5.72 g of TERGITOL15-S-40 (100%), 95.21 g of methyl methacrylate, 157.23 g of styrene,183.02 g of 2-ethylhexyl acrylate, and 1.31 g of trimethylolpropanetriacrylate was begun at 5.25 g/min. After the first emulsion feed wascompleted, the lines were rinsed with 60 g of water, and heatingcontinued. After 25 minutes, a second emulsion feed composed of 138 g ofwater, 8.74 g of AEROSOL 18, 2.85 g of TERGITOL 15-S-40 (100%), 225.8 gof styrene, 153.5 g of 2-ethylhexyl acrylate, 47.97 g ofacetoacetoxyethyl methacrylate, 28.78 g of allyl methacrylate, 18.81 gof dimethylaminoethyl methacrylate, and 4.894 g of 2-ethylhexyl3-mercaptopropionate was started at 8 g/minute. Ten minutes after thefeeds were completed, the reactor was cooled to 65° C., then aninitiator solution composed of 2.74 g of sodium formaldehyde sulfoxylatedissolved in 32.2 g of water, and 5.05 g of a catalyst solution composedof 0.5% iron (II) sulfate chelated with ethylenediamine tetracetic acidwere added to the reactor. A solution of 2.94 g of t-butylhydroperoxidedissolved in 32.2 g of water was fed into the reactor over 15 minutes.The latex was then filtered through 100 mesh wire screen. Solids level,46.9; pH, 7.6; amount of dried material (100 mesh screen), 2.0 g;particle size (Dw), 197 nm.

EXAMPLE 18 Preparation of a Small Particle Size, Core/ShellAmine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 720.4 g of water, 39.2 g of HITENOLHS-20, 1.08 g of TERGITOL 15-S-40 (100%), 5.84 g of sodium carbonate,26.14 g of methyl methacrylate, 35.2 g of styrene, 26.4 g of2-ethylhexyl acrylate, and 0.264 g of trimethylolpropane triacrylate. Anitrogen purge was begun, then the contents of the reactor brought up to80° C. at 400 rpm. After reaching 80° C., an initiator solution composedof 6.16 g of sodium persulfate dissolved in 34.84 g of water was addedto the reactor. An initiator solution composed of 2.08 g of sodiumpersulfate dissolved in 53.6 g of water was started at 0.336 g/min.Thirty minutes after the initiator feed was begun, an emulsion feedcomposed of 158.4 g of water, 15.72 g of AEROSOL 18, 11.00 g of TERGITOL15-S-40 (100%), 110.4 g of methyl methacrylate, 148.7 g of styrene,111.52 g of 2-ethylhexyl acrylate, and 1.12 g of trimethylolpropanetriacrylate was begun at 5.24 g/min. After the first emulsion feed wascompleted, the feed lines were washed with 80 g of water, and thetemperature held at 80° C. for 30 minutes. The reactor was then cooledto 65° C., and an initiator solution of 2.74 g of sodium formaldehydesulfoxylate dissolved in 16 g of water, and 5.05 g of a catalystsolution composed of 0.5% iron (II) sulfate chelated withethylenediamine tetracetic acid were added to the reactor. A secondemulsion feed composed of 138.4 g of water, 9.72 g of AEROSOL 18, 6.99 gof TERGITOL 15-S-40 (100%), 191.90 g of styrene, 43.25 g of methylmethacrylate, 143.92 g of 2-ethylhexyl acrylate, 95.95 g ofacetoacetoxyethyl methacrylate, and 9.45 g of the sodium2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 5.24g/min. A solution of 3.92 g of t-butylhydroperoxide dissolved in 32 g ofwater was fed into the reactor during the second emulsion feed at 0.14g/min. After the t-butylhydroperoxide feed was completed, heating wascontinued for 30 minutes. The emulsion was cooled to less than 35° C.,and 122 g of polyethylenimine (50%) were pumped in over 15 minutes. Thelatex was then filtered through 100 mesh wire screen. Solids level,44.6; amount of dried material (100 mesh screen), 1.1 g; particle size(Dw), 54 nm; pH, 10.5. Infrared analysis of clear films cast over ZnSeshowed an absorption at 1565 cm⁻¹ which represents an enamine moiety.

EXAMPLE 19 Preparation of Pigment Grind

A pigment grind was prepared using a Premier disperser, as below, and aportion of the grind was used to letdown each specified paint.

    ______________________________________                                        Material:         Volume:                                                     ______________________________________                                        Deionized (DI) Water                                                                            120.0                                                         TAMOL 1124 dispersant 12.0                                                    TRITON CF-10 6.0                                                              Propylene Glycol 6.0                                                          FOAMASTER AP 6.0                                                            ______________________________________                                    

The materials were dispersed well and then was added under agitation:

    ______________________________________                                               TI-PURE R-900                                                                           600.0                                                        ______________________________________                                    

After Cowles until the grind passed 7+ Hegman, then water was added:

    ______________________________________                                                Water 37.5                                                            ______________________________________                                    

EXAMPLE 20 Preparation of a Pigmented Coating Formulation using Latexfrom Example 17

Paint Letdown:

    ______________________________________                                        Material:         Weight (g):                                                 ______________________________________                                        Latex             Example 17                                                    Example 19 Grind 137.02                                                       Example Latex 216.0                                                           TEXANOL 6.5                                                                   FOAMASTER AP)Premix 1.04                                                      FOAMASTER VF) 1.56                                                            5% Cobalt Hydrocure II) 2.34                                                ______________________________________                                    

The above were mixed with stirring then the following were added:

    ______________________________________                                        RHOPLEX RM 2020    56.16                                                        (50% aqueous by weight)                                                       DI (deionized) Water 39.0                                                     Ammonia 0.8                                                                   (28% aqueous by weight)                                                       RHEOVIS CR2 thickener 24.26                                                   (60% aqueous by weight)                                                       Resulting pH: 8.55                                                            Paint Viscosity (KU): 88                                                      ICI Viscosity (P): 2.09                                                       Brookfield Viscosity* (cP): 5,760                                           ______________________________________                                         *spindle 3 at 3 rpm                                                      

Paint viscosity (in Krebs Units) was measured after 24 hours using aKrebs-Stormer viscometer. The resulting paint, Example 20, was evaluatedfor gloss, color, scrub resistance, alkali resistance, blockingresistance, and print resistance. The results are shown in the followingTables 1-5.

                  TABLE 1                                                         ______________________________________                                                                   BT/TF                                                  Scrub Days Wet Adhesion Alkali                                              Gloss Color Dry Days/Dry Resist 7D                                          Paint                                                                              60/20  L,a,b   1D   7D    1D    7D     Dry                               ______________________________________                                        20   73/31  95.17,  89   277   87/181                                                                              865/2311                                                                             6.5%                                  -0.39,                                                                        2.21                                                                      ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Blocking Resistance: Days (D) dry-Days (D) Face-To-Face (FTF)                   Paint   1D-1D    1D-7D 2D-1D  2D-7D 7D-1D  7D-7D                            ______________________________________                                          20 4 3 4 4 5 4                                                              ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Blocking Resistance: Days (D) dry-30 Minutes FTF at 120° F.                Paint  1D             2D   7D                                             ______________________________________                                          20 1 2 4                                                                    ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Print Resistance: Days (D) dry-Days (D) Face-To-Face (FTF)                      Paint   1D-1D    1D-7D 2D-1D  2D-7D 7D-1D  7D-7D                            ______________________________________                                          20 2 2 4 4 4 2                                                              ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Paint Resistance: Days (D) dry-30 Minutes FTF at 120° F.                   Paint  1D             2D   7D                                             ______________________________________                                          20 4 6 6                                                                    ______________________________________                                    

EXAMPLE 21 Preparation of a Small Particle Size, Core/ShellAcetoacetoxy-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 720 g of water, 39.2 g of HITENOL HS-20,1.54 g of TERGITOL NP-40 (70%), 5.84 g of ammonium bicarbonate, 26.14 gof methyl methacrylate, 35.2 g of styrene, 26.4 g of 2-ethylhexylacrylate, and 0.264 g of trimethylolpropane triacrylate. A nitrogenpurge was begun, then the contents of the reactor brought up to 80° C.at 400 rpm. After reaching 80° C., an initiator solution composed of6.16 g of ammonium persulfate dissolved in 34.84 g of water was added tothe reactor. An initiator solution composed of 2.08 g of ammoniumpersulfate dissolved in 53.6 g of water was started at 0.336 g/min.Thirty minutes after the initiator feed was begun, an emulsion feedcomposed of 153.6 g of water, 15.72 g of AEROSOL 18, 15.72 g of TERGITOLNP-40 (70%), 110.4 g of methyl methacrylate, 148.7 g of styrene, 111.52g of 2-ethylhexyl acrylate, and 1.12 g of trimethylolpropane triacrylatewas begun at 5.24 g/min. After the first emulsion feed was completed,the feed lines were washed with 80 g of water, and the temperature heldat 80° C. for 30 minutes. The reactor was then cooled to 65° C., and aninitiator solution of 2.74 g of sodium formaldehyde sulfoxylatedissolved in 16 g of water, and 5.05 g of a catalyst solution composedof 0.5% iron (II) sulfate chelated with ethylenediamine tetracetic acidwere added to the reactor. A second emulsion feed composed of 138.4 g ofwater, 9.72 g of AEROSOL 18, 9.98 g of TERGITOL NP-40 (70%), 191.90 g ofstyrene, 45.6 g of methyl methacrylate, 143.92 g of 2-ethylhexylacrylate, 95.95 g of acetoacetoxyethyl methacrylate, and 4.72 g of thesodium 2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at5.24 g/min. A solution of 3.92 g of t-butylhydroperoxide dissolved in 32g of water was fed into the reactor during the second emulsion feed at0.14 g/min. After the t-butylhydroperoxide feed was completed, heatingwas continued for 30 minutes. The latex was then filtered through 100mesh wire screen. Solids level, 44.9; amount of dried material (100 meshscreen), 1.5 g; particle size (Dw), 72 nm.

EXAMPLE 22 Preparation of a Small Particle Size, Core/ShellAmine-Containing Waterborne Polymer

To a 400 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 900 g of water, 49 g of HITENOL HS-20,1.93 g of TERGITOL NP-40 (70%), 7.3 g of sodium carbonate, 32.67 g ofmethyl methacrylate, 44 g of styrene, 33 g of 2-ethylhexyl acrylate, and0.33 g of trimethylolpropane triacrylate. A nitrogen purge was begun,then the contents of the reactor brought up to 80° C. at 400 rpm. Afterreaching 80° C., an initiator solution composed of 7.70 g of sodiumpersulfate dissolved in 43.55 g of water was added to the reactor. Aninitiator solution composed of 2.61 g of sodium persulfate dissolved in67 g of water was started at 0.42 g/min. Thirty minutes after theinitiator feed was begun, an emulsion feed composed of 192 g of water,19.65 g of AEROSOL 18, 19.65 g of TERGITOL NP-40 (70%), 138.01 g ofmethyl methacrylate, 185.88 g of styrene, 139.41 g of 2-ethylhexylacrylate, and 1.394 g of trimethylolpropane triacrylate was begun at6.56 g/min. After the first emulsion feed was completed, the feed lineswere washed with 80 g of water, and the temperature held at 80° C. for30 minutes. The reactor was then cooled to 65° C., and an initiatorsolution of 3.42 g of sodium formaldehyde sulfoxylate dissolved in 20 gof water, and 6.31 g of a catalyst solution composed of 0.5% iron (II)sulfate chelated with ethylenediamine tetracetic acid were added to thereactor. A second emulsion feed composed of 173 g of water, 12.15 g ofAEROSOL 18, 12.48 g of TERGITOL NP-40 (70%), 239.88 g of styrene, 54.06g of methyl methacrylate, 179.91 g of 2-ethylhexyl acrylate, 119.94 g ofacetoacetoxyethyl methacrylate, and 11.81 g of the sodium2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at 6.56g/min. A solution of 4.9 g of t-butylhydroperoxide dissolved in 40 g ofwater was fed into the reactor during the second emulsion feed at 0.14g/min. After the t-butylhydroperoxide feed was completed, heating wascontinued for 30 minutes. The emulsion was cooled to less than 35° C.,and 202.53 g of polyethylenimine (50%) were pumped in over 15 minutes.The latex was then filtered through 100 mesh wire screen. Solids level,44.7; amount of dried material (100 mesh screen), 1.3 g; particle size(Dw), 56 nm; pH, 10.5.

EXAMPLE 23 Preparation of a Small Particle Size, UnstructuredAmine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 1115 g of water, 15.52 g of HITENOLHS-20, 2.55 g of TERGITOL NP-40 (70%), 3.5 g of sodium carbonate, 8.10 gof methyl methacrylate, 5.38 g of 2-ethylhexyl acrylate, and 4.43 ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator charge composed of 2.30 g of sodium persulfatedissolved in 13.0 g of water was added to the reactor. An emulsion feedcomposed of 120 g of water, 6.55 g of AEROSOL 18, 10.22 g of TERGITOLNP-40 (70%), 66.36 g of methyl methacrylate, 170.73 g of 2-ethylhexylacrylate, and 101.0 g of acetoacetoxyethyl methacrylate was begun at8.38 g/min. Five minutes after the first emulsion feed was begun, aninitiator solution composed of 1.3 g of sodium persulfate dissolved in33.5 g of water was fed at 0.536 g/min. Five minutes after the monomeremulsion feed was completed, a post initiator solution of 3.125 g ofsodium persulfate and 3.125 g of sodium metabisulfite g of sodiummetabisulfite dissolved in 93.8 g of water was charged and heatingcontinued for 30 minutes. The emulsion was cooled to 30° C., then 299.4g of polyethylenimine (33.3% solids in water) was added to the reactorand stirring continued for 15 minutes. The latex was then filteredthrough 100 mesh wire screen. Solids level, 23.9; amount of driedmaterial (100 mesh screen), 0.00 g; particle size, 53 nm. Glasstransition onset/midpoint, -14° C./4° C. Infrared analysis of clearfilms cast over ZnSe showed absorptions at 1552 cm⁻¹ and 1597 cm⁻¹ whichrepresent the formation of enamine moieties from the reaction betweenpolyethylenimine and acetoacetoxy moieties.

EXAMPLES 24-35 Preparation of Small Particle Size, UnstructuredAmine-Containing Waterborne Polymers

The monomer compositions were the same as described in Example 23. Theprocess was similar to that described in Example 23 except for solidlevels adjustments, surfactant changes, levels of poly(ethylenimine) andprocess changes described in Table 6. Using the data from Table 6, FIG.1 illustrates the relationship between polymer particle size, percentsolids, and viscosity of these latexes. As can be seen from Table 6 andfrom FIG. 1, a latex according to the invention having a small polymerparticle size of nearly 60 nm and a 50% solids level, still possesses alatex viscosity of less than 200 cps.

                                      TABLE 6                                     __________________________________________________________________________    Characterization of Examples 23-35                                                                                     Tg, onset/                               Grams of H.sub.2 O in Recoverable Particle Viscosity, Grams of PEI                                                 midpoint                               Examples Solids Reactor Charge Solids (g) Size (nm) cps (60 rpm) (%                                                  Solids) (° C.)                __________________________________________________________________________    23   23.9                                                                              1115    0.00  53   5.5   299.4 (33.3)                                                                         -14/4                                  .sup. 24.sup.a 24.1 1115 0.00 53 6.1 299.4 (33.3) -13/3                       .sup. 25.sup.b 24.1 1100 0.00 55 5.4 299.4 (33.3)  -7/8                       26 31.3 650 0.00 59 9.5 299.4 (33.3) -31.4 (calc'd)                           27 31.5 650 0.00 53 9.8 299.4 (33.3) -16/-7                                   28 36.1 450 0.00 45 16.8 299.4 (33.3) -18/-8                                  29 35.9 440 2.08 55 14.9 299.4 (33.3) -18/-7                                  30 41.6 340 0.00 52 42.6 235.4 (42.5) -17/-6                                  31 43.5 290 0.00 67 66.2 221.5 (45)   -16/-7                                  32 44.2 290 0.00 59 79.2 199.4 (50)   -17/-8                                  33 44.6 290 1.74 59 72.5 199.4 (50)   -18/-9                                  34 50.2 190 2.53 90 --  0.sup.c -36 (calc'd)                                  35 50.1 190 1.79 60 179.0 199.4 (50)   -31 (calc'd)                         __________________________________________________________________________     .sup.a PEI was added with stirring into the latex at 60° C.            .sup.b Used 38.8 g of TREM LF40 as the reactive surfactant instead of         HITENOL HS20                                                                  .sup.c Used 31.7 g of ammonium hydroxide solution (28% active in water) i     place of PEI.                                                            

EXAMPLE 36 Preparation of a Small Particle Size, UnstructuredAmine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 1115 g of water, 15.52 g of HITENOLHS-20, 2.55 g of TERGITOL NP-40 (70%), 3.5 g of sodium carbonate, 8.98 gof styrene, 3.62 g of 2-ethylhexyl acrylate, and 5.32 g ofacetoacetoxyethyl methacrylate. A nitrogen purge was begun, then thecontents of the reactor brought up to 80° C. at 400 rpm. After reaching80° C., an initiator charge composed of 2.30 g of sodium persulfatedissolved in 13.0 of water was added to the reactor. An emulsion feedcomposed of 120 g of water, 9.94 g of AEROSOL 18, 10.22 g of TERGITOLNP-40 (70%), 170.39 g of styrene, 68.70 g of 2-ethylhexyl acrylate, and101.0 g of acetoacetoxyethyl methacrylate was begun at 8.38 g/min. Fiveminutes after the first emulsion feed was begun, an initiator solutioncomposed of 1.3 g of sodium persulfate dissolved in 33.5 g of water wasfed at 0.536 g/min. Five minutes after the monomer emulsion feed wascompleted, a post initiator solution of 3.125 g of sodium persulfate and3.125 g of sodium metabisulfite dissolved in 93.8 g of water was chargedand heating continued for 30 minutes. The emulsion was cooled to 30° C.,then 299.4 g of polyethylenimine (33.3% solids in water) was added tothe reactor and stirring continued for 15 minutes. The latex was thenfiltered through 100 mesh wire screen. Solids level, 23.8; amount ofdried material (100 mesh screen), 0.00 g; particle size, 49 nm. Infraredanalysis of clear films cast over ZnSe showed absorptions at 1553 cm⁻¹and 1597 cm⁻¹ which represent the formation of enamine moieties from thereaction between polyethylenimine and acetoacetoxy moieties.

EXAMPLES 37-44 Preparation of a Small Particle Size, UnstructuredAmine-Containing Waterborne Polymer

The monomer compositions were the same as described in Example 36. Theprocess was similar to that described in Example 36 except for solidlevels adjustments, surfactant changes, levels of poly(ethylenimine) andprocess changes described in Table 7.

                                      TABLE 7                                     __________________________________________________________________________    Characterization of Examples 36-44                                                     Grams of H.sub.2 O in                                                                 Recoverable                                                                         Particle                                                                           Viscosity,                                                                          Grams of PEI                                  Examples Solids Reactor Charge Solids (g) Size (nm) cps (60 rpm) (%                                           Solids)                                     __________________________________________________________________________    36   23.9                                                                              1115    0.00  49   5.9   299.4 (33.3)                                  37.sup.a 23.8 1100  48.6 48 5.7 299.4 (33.3)                                  38 30.8 650 0.37 62 9.9 299.4 (33.3)                                          39 31.3 650 0.45 54 10.2 299.4 (33.3)                                         40 37.0 340 0.28 56 30.9 262.4 (38.0)                                         41 41.8 340 0.00 55 30.0 235.4 (42.5)                                         42 43.7 290 0.00 58 46.6 221.5 (45)                                           43 45.0 290 <5 54.5 41.3 199.4 (50)                                           44 43.7 290 4.8 51.5 89.7  0.00                                             __________________________________________________________________________     .sup.a. Used 38.8 g of TREM LF40 as the reactive surfactant instead of        HITENOL HS20.                                                            

EXAMPLE 45 Film Properties

Clear films were prepared using the latexes of Examples 24, 25, 27, and28. Clear films were cast on release paper and cured ambiently forspecified periods of time in the CTH room or cured for 30 minutes in aforced air oven at 120° C. The film tensile properties, film gelfraction (FGF), film swell ratio (FSR), and volatile content weredetermined. The results are shown in Table 8 below. The changes observedin ambient versus thermal (120° C.) curving demonstrate the curingbehavior of the films.

                                      TABLE 8                                     __________________________________________________________________________                       Tensile Properties                                                    Film (in acetone)                                                                     Ultimate                                                                           Ultimate    Initial                                                                            Yield                                                                              Yield                                Drying                                                                              Swell                                                                             Gel Breaking                                                                           Elongation:                                                                         Work: Modulus                                                                            Breaking                                                                           Elongation:                       Example Conditions Ratio Fraction Load (psi) (%) (in ·                                                           lb/in.sup.3) (ksi) Load                                                       (psi) (%)                       __________________________________________________________________________    24   8 days CTH                                                                          3.7 83.5                                                                              1422 145.1 1242  3.4  309  17.9                               120° C., 30" 2.9 93.4  683 168.6 767 4.3 161 11.2                     25 8 days, CTH 3.9 82.9 1496 129.5 1012  2.8 302 20.5                          120° C., 30" 2.7 94.6  496 110.2 328 3.0 120 11.5                     27 8 days, CTH 3.2 88.7 1708 117.4 867 3.1 298 20.7                            120° C., 30" 3.0 93.5 1153 102.4 590 4.5 249 14.3                     28 8 days, CTH 3.4 85.0  453 35.8 104 4.3 186 10.6                             120° C., 30" 3.1 93.4  811 87.7 341 2.5 169 15.4                    __________________________________________________________________________

EXAMPLE 46 Residual Monomer Reduction

Three AAEM acetoacetoxy-based latexes having average residual level ofethyl acrylate was 50 ppm, and the amount of acetone (from hydrolysis ofAAEM during polymerization) detected in the latex was 0.13%. Sampleswere prepared by blending each latex with a PPAE latex (3 parts latex to1 part PPAE latex). The PPAE latex contained no ethyl acrylate as a basemonomer and 0.08% acetone. After one week, the amount of detectableethyl acrylate and acetone in all three samples was 2 ppm (theoretical:37 ppm) and the amount of detectable acetone, 0.006% (theoretical0.11%), respectively. The results demonstrate the ability of a PPAEaccording to the invention to scavenge or remove carbonyl-basedcompounds, such as acrylates, ketones, aldehydes, acrylonitrile, andvinyl acetate from complex compositions such as waterborne polymerlatexes.

EXAMPLE 47 (COMPARATIVE)

Preparation of latex described in European Patent Application, 0 634 425A1, Example 10 Latex B (Composition: Core: ButylAcrylate/Styrene/Divinyl Benzene/Methacrylic Acid; 3/91.6/4.4/1 Shell:Butyl Acrylate/Acetoacetoxyethyl Methacrylate/Methacrylic Acid; 83/10/7)

To a 1000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 382.5 g of water, 0.072 g of AEROSOL OT(75%), 0.1 g of TERGITOL 15-S-40 (70%), 0.1761 g of methacrylic acid,16.13 g of styrene, 0.528 g of butyl acrylate, and 0.775 g of divinylbenzene. A nitrogen purge was begun, then the contents of the reactorbrought up to 80° C. at 400 rpm. After reaching 80° C., an initiatorsolution composed of 2.26 g of sodium persulfate dissolved in 13.06 g ofwater was added to the reactor. An emulsion feed composed of 57.45 g ofwater, 0.765 g of AEROSOL OT (75%), 0.765 g of TERGITOL 15-S-40 (70%),1.55 g of methacrylic acid, 141.8 g of styrene, 4.64 g of butylacrylate, and 6.81 g of divinyl benzene was begun at 2 g/min. Fiveminutes after the first emulsion feed was begun, an initiator solutioncomposed of 1.278 g of sodium persulfate dissolved in 32.7 g of waterwas fed at 0.466 g/min. Thirty minutes after the first emulsion feed wascompleted, the reactor was cooled to 75° C., and a second feed composedof 0.21 g of AEROSOL OT (75%), 0.21 g of TERGITOL 15-S-40 (70%), 149.32g of butyl acrylate, 17.99 g of acetoacetoxyethyl methacrylate, and12.59 of the methacrylic acid was fed at 2.0 g/min. Five minutes afterthe last feed, the reactor was cooled to 65° C., and 0.6 g of a 0.5%Fe(II) sulfate solution complexed with EDTA, and 0.39 g of isoascorbicacid dissolved in 6 g of water were charged to the reactor. An feedsolution prepared from 0.288 g of t-butylhydroperoxide (70%) dissolvedin 6 g of water was then fed into the reactor over 30 minutes. After theinitiator feed, heating was continued for 30 minutes, then the emulsionwas cooled. The latex was then filtered through 100 mesh wire screen.Solids level, 45%.

EXAMPLE 48 (COMPARATIVE)

Attempted Functionalization of Latex from Example 47 withPolyethylenimine using the process described in Example 10, Latex B,European Patent Application, 0 634 425 A1

To 104 g of the latex from Example 46 was successively added whilestirring the latex at room temperature 8.93 g of butyl CELLOSOLVE,(available from Union Carbide, Houston, Tex.), 2.98 g of butyl CARBITOL(available from Union Carbide, Houston, Tex.), and 0.37 g ofpolyethylenimine (PEI, 50% in water). The latex began to coagulate.After adding a total of 0.97 g of polyethylenimine (PEI, 50% in water),the latex had completely coagulated forming a solid mass.

                                      TABLE 9                                     __________________________________________________________________________    PEI    PEI    Moles of                                                          (50% solution), (dry material), Acetoacetoxy Moieties Active Moles of                                         N-H Mole Ratio of N-H                         g g per 104 g of latex Moieties from PEI per Acetoacetoxy                   __________________________________________________________________________      0.37 0.185 0.011 0.0043 0.39                                                  0.97 0.485 0.011 0.0011 1.0                                                 __________________________________________________________________________

EXAMPLE 49 Preparation of a Small Particle Size, Core/ShellEnamine-Containing Waterborne Polymer

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 900.5 g of water, 49.0 g of HITENOLHS-20, 1.35 g of TERGITOL 15-S-40, 7.3 g of sodium carbonate, 31.9 g ofmethyl methacrylate, 44 g of styrene, 33 g of 2-ethylhexyl acrylate, and1.1 g of trimethylolpropane triacrylate. A nitrogen purge was begun,then the contents of the reactor brought up to 80° C. at 400 rpm. Afterreaching 80° C., an initiator charge composed of 7.54 g of sodiumpersulfate dissolved in 43.6 g of water was added to the reactor. Anemulsion feed composed of 198 g of water, 19.65 g of AEROSOL 18, 13.8 gof TERGITOL 15-S-40, 134.8 g of methyl methacrylate, 185.9 g of styrene,139.4 g of 2-ethylhexyl acrylate, and 4.6 g of trimethylolpropanetriacrylate was begun at 8.38 g/min. Five minutes after the firstemulsion feed was begun, an initiator solution composed of 4.26 g ofsodium persulfate dissolved in 109 g of water was fed at 0.466 g/min.After the first emulsion feed was completed, a second emulsion feedcomposed of 173 g of water, 12.15 g of AEROSOL 18, 8.7 g of TERGITOL15-S-40, 239.4 g of styrene, 54.1 g of methyl methacrylate, 179.9 g of2-ethylhexyl acrylate, 119.9 g of acetoacetoxyethyl methacrylate, and11.8 g of the sodium 2-acrylamido-2-methylpropanesulfonate (50% inwater) was fed at 8.38 g/min. Five minutes after the last feed, aninitiator solution of 0.95 g of t-butyl hydroperoxide (70%), 1.34 g ofisoascorbic acid dissolved in 20 g of water, and 2 g of 0.5% iron(II)sulfate.7 H₂ 0 (chelated with EDTA) was charged and heating continuedfor 30 minutes. The emulsion was cooled, and 35.8 g of ammoniumhydroxide (28%) were pumped in over 15 minutes. The latex was thenfiltered through 100 mesh wire screen. Solids level, 43.5; amount ofdried material (100 mesh screen), 0.94 g; particle size (Dw), 60 nm.Infrared analysis of clear films cast over ZnSe showed an absorption at1565 cm⁻¹ which represents an enamine moiety.

EXAMPLE 50 Preparation of Low Gloss Formulated Coatings

    ______________________________________                                                         Formula 50A                                                                             Formula 50B                                          Material: Weight: (g) Weight (g):                                           ______________________________________                                        GRIND:                                                                          DI Water 28.0 28.0                                                            TAMOL 1124 2.6 2.6                                                            TRITON CF-10 1.3 1.3                                                          FOAMASTER AP 1.3 1.3                                                          DOWICIL 75 0.5 0.5                                                          Mix well then add under agitation:                                                TI-PURE R-900    99.0      99.0                                             OmyaCarb UF 31.0 31.0                                                       Cowles until the grind passes 6 Hegman, then add:                                 DI Water         15.5      15.5                                             LETDOWN:                                                                      Grind (above) 179.2 179.2                                                     Emulsion: Example 48 231.0 231.0                                              Premix*:                                                                      *Foamaster AP 3.4 3.4                                                         *Foamaster VF 1.3 1.3                                                         *Aerosol OT-75 0.4 0.4                                                        *Eastman EB 4.8 4.8                                                           *Eastman DB 4.8 4.8                                                           Eastman EB 2.0 4.0                                                            Eastman DB 2.0 4.0                                                            DI Water 9.5 4.0                                                              RM-2020 Solution 54.0 --                                                      Tafigel PUR 45 Solution --  10.0                                            Adjust viscosity to approx 85 KU with the following                               CR2 Thickener    44.7      62.0                                             Final pH: 8.8 8.8                                                             Final KU: 82 79                                                             ______________________________________                                    

The resulting paints, Examples 49A and 49B, were evaluated for gloss,wet adhesion, scrub resistance, blocking resistance, and printresistance. The results are shown in the following Table 10-14.

                  TABLE 10                                                        ______________________________________                                        Gloss    Scrub Average of 8,                                                                         BT/TF Wet Adhesion Days/Dry                            Paint                                                                              60/20   15, & 21 Days Dry                                                                           1 D      7 D                                       ______________________________________                                        49A  41/7    648           1800/3000                                                                              3000/3000                                   49B 17/3 695 3000/3000 3000/3000                                            ______________________________________                                    

                                      TABLE 11                                    __________________________________________________________________________    Blocking Resistance: Days (D) dry - Days (D) Face-To-Face (FTF)               Paint                                                                            1 D--1 D                                                                           1 D-7 D                                                                            2 D-1 D                                                                            2 D-7 D                                                                            7 D-1 D                                                                            7 D--7 D                                                                           21 D-1 D                                                                           21 D-7 D                                __________________________________________________________________________    49A                                                                              9    7    7    9    9    9    10   10                                        49B 8 6 9 6 6 7 10  9                                                       __________________________________________________________________________

                  TABLE 12                                                        ______________________________________                                        Paint                                                                              Blocking Resistance: 21 Days (D) dry - 30 Minutes FTF at 120°          F.                                                                       ______________________________________                                        49A  7                                                                          49B 10                                                                      ______________________________________                                    

                                      TABLE 13                                    __________________________________________________________________________    Print Resistance: Days (D) dry - Days (D) Face-To-Face (FTF)                  Paint                                                                            1 D--1 D                                                                           1 D-7 D                                                                            2 D-1 D                                                                            2 D-7 D                                                                            7 D-1 D                                                                            7 D--7 D                                                                           21 D-1 D                                                                           21 D-7 D                                __________________________________________________________________________    49A                                                                              0    0    1    1    7    4    8    7                                         20 6 2 3 3 7 3 6 3                                                          __________________________________________________________________________

                  TABLE 14                                                        ______________________________________                                        Paint                                                                              Print Resistance: 21 Days (D) dry - 30 Minutes FTF at 120°        ______________________________________                                             F.                                                                       49A  8                                                                          49B 10                                                                      ______________________________________                                    

EXAMPLE 51 Preparation of Small Core/shell Amine-functional Particle

To a 3000 mL resin kettle equipped with a condenser, nitrogen purge, andsubsurface feed tube were added 720.4 g of water, 39.2 g of HITENOLHS-20, 1.59 g of TERGITOL NP-40 (70%), 25.5 g of methyl methacrylate,35.2 g of styrene, 26.4 g of 2-ethylhexyl acrylate, 0.88 g oftrimethylolpropane triacrylate and 5.84 g of sodium carbonate. Anitrogen purge was begun, then the contents of the reactor brought up to80° C. at 400 rpm. After reaching 80° C., an initiator charge composedof 6.0 g of sodium persulfate dissolved in 34.84 g of water was added tothe reactor. An emulsion feed composed of 197.2 g of water, 15.72 g ofAEROSOL 18, 16.18 g of TERGITOL 15-S-40 (70% in water), 107.81 g ofethyl methacrylate, 148.70 g of styrene, 111.53 g of 2-ethylhexylacrylate, and 3.72 of trimethylolpropane triacrylate was begun at5.248/min. Five minutes after the first emulsion feed was begun, aninitiator solution composed of 3.41 g of sodium persulfate dissolved in87.2 g of water was fed at 0.336 g/min. After the first emulsion feed ascompleted, the feed line was washed with 20 g of water and the eactionwas held at 80° C. for 30 minutes. Then a second emulsion feed composedof 135.2 g of water, 9.72 g of AEROSOL 18, 10.28 g of TERGITOL 15-S-40(68% in water), 191.90 g of styrene, 43.25 g of methyl methacrylate,143.93 g of 2-ethylhexyl acrylate, 95.95 g of acetoacetoxyethylmethacrylate, and 9.45 g of the sodium2-acrylamido-2-methylpropanesulfonate (50% in water) was fed at5.25/min. After the last feed, the reaction was held for 10 minutes at80° C. then cooled to 65° C. over the next 20 minutes The reactor wasthen charged with a solution of 0.8 g of isoascorbic acid in 16 g waterand 0.4 g of 0.5% iron (II) sulfate. Over the next 30 minutes, asolution of 0.58 g of t-butyl hydroperoxide (70% in water) in 16 g ofwater was fed into the reactor while heating continued. The emulsion wascooled, then 174.76 g of poly(ethylenimine) LUPASOL G35 (50% in water)was fed into the emulsion and the emulsion was filtered through 100 meshwire screen. Dried solids collected on 100 mesh screen=1.24 g. Totalsolids level of 45% and pH was 10.4.

EXAMPLE 52 Addition of 10% Sulfuric Acid to Example 51 Latex to Make aCationic System

16.92 g water was added to 15.0 g ice, the 3.58 g of concentratedsulfuric acid was added to the ice and water mixture to make a 10%olution of sulfuric acid. With stirring, the entire 10% sulfuric acidolution was added slowly to 50 g of the amine-functional latex ofExample 51. The latex appeared to raise in viscosity very slightly uponinitial contact but redispersed very nicely as the remainder of thesulfuric acid was added. Final pH=0.9, particle size 105 nm.

The claimed invention is:
 1. A surfactant-containingacetoacetoxy-functional polymer comprising the reaction product of thefree radical polymerization of a non-acid vinyl monomer having anacetoacetoxy-type functionality with at least one non-self-polymerizing,ethylenically-unsaturated surfactant monomer selected from the groupconsisting of a sodium alkyl allyl sulfosuccinate and a polyoxyethylenealkyl phenyl ether of formula (3), (4), or (5): ##STR2## where R isnonyl or octyl, n ranges from 15 to 50, and m ranges from 15 to
 40. 2. Apolymer of claim 1, comprising about 1 to about 40 weight percent of thenon-acid vinyl monomer having an acetoacetoxy-type functionality ofFormula (1):

    R.sup.1 --CH═C(R.sup.2)C(O)--X.sup.1 --X.sup.2 --X.sup.3 --C(O)--CH.sub.2 --C(O)--R.sup.3                          ( 1)

where R¹ is a hydrogen or halogen; R² is a hydrogen, halogen, C₁ -C₆alkylthio group, or C₁ -C₆ alkyl group; R³ is a C₁ -C₆ alkyl group; X¹and X³ are independently O, S, or a group of the formula --N(R')--, inwhich R' is a C₁ -C₆ alkyl group; X² is a C₁ -C₁₂ alkylene group or C₃-C₁₂ cycloalkylene group; about 0.05 to about 20 weight percent of theat least one non-self-polymerizing, ethylenically-unsaturated surfactantmonomer; and about 75 to about 90 weight percent of a non-acid vinylmonomer.
 3. A polymer of claim 2, wherein the monomer of Formula (1) isselected from the group consisting of acetoacetoxyethyl methacrylate;acetoacetoxyethyl acrylate; acetoacetoxy(methyl)ethyl acrylate;acetoacetoxypropyl acrylate; allyl acetoacetate; acetoacetamidoethyl(meth)acrylate; and acetoacetoxybutyl acrylate, and wherein the non-acidvinyl monomer is selected from the group consisting of methyl acrylate;methyl methacrylate; ethyl acrylate; ethyl methacrylate; butyl acrylate;butyl methacrylate; isobutyl acrylate; isobutyl methacrylate; ethylhexylacrylate; 2-ethylhexyl methacrylate; octyl acrylate; octyl methacrylate;iso-octyl acrylate; iso-octyl methacrylate; trimethylolpropyltriacrylate; styrene; α-methyl styrene; glycidyl methacrylate;carbodiimide methacrylate; C₁ -C₁₈ alkyl crotonates; di-n-butyl maleate;di-octylmaleate; allyl methacrylate; di-allyl maleate; di-allylmalonate;methoxybutenyl methacrylate; isobornyl methacrylate; hydroxybutenylmethacrylate; hydroxyethyl (meth)acrylate; hydroxypropyl (meth)acrylate;acrylonitrile; vinyl chloride; ethylene; vinyl ethylene carbonate; epoxybutene; 3,4-dihydroxybutene; hydroxyethyl (meth)acrylate; sodium2-acrylamido-2-methylpropane sulfonate; methacrylamide; acrylamide;butyl acrylamide; ethyl acrylamide; vinyl (meth)acrylate; isopropenyl(meth)acrylate; cycloaliphaticepoxy (meth)acrylates; vinylformamide;2,3-dihydrofuran a vinyl ester of Formula (2):

    RCH═CH--O--C(O)--C(R).sub.3                            ( 2)

wherein R is independently hydrogen or an alkyl group of up to 12 carbonatoms; t-butylaminoethyl methacrylate; dimethylaminoethyl methacrylate;diethylaminoethyl methacrylate; N,N-dimethylaminopropyl methacrylamide;2-t-butylaminoethyl methacrylate; N,N-dimethylaminoethyl acrylate;N-(2-methacrylamidoethyl)ethylene urea; andN-(2-methacryloyloxyethyl)ethylene urea.
 4. A polymer of claim 1,wherein the polymer is a structured particle having an average polymerparticle size ranging from about 25 to about 500 nm.
 5. A polymer ofclaim 1, wherein the polymer is an unstructured particle having anaverage polymer particle size ranging from about 25 to about 500 nm.